CN103129064B - Hard coating film, transparent conductive laminate and touch panel - Google Patents

Hard coating film, transparent conductive laminate and touch panel Download PDF

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Publication number
CN103129064B
CN103129064B CN201210499264.7A CN201210499264A CN103129064B CN 103129064 B CN103129064 B CN 103129064B CN 201210499264 A CN201210499264 A CN 201210499264A CN 103129064 B CN103129064 B CN 103129064B
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China
Prior art keywords
hard conating
hard
coating film
hard coating
conating
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CN103129064A (en
Inventor
赤松正
远藤大士
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EWA Co Ltd
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EWA Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

The object of this invention is to provide hard coating film, transparent conductive laminate and touch panel, there is excellent hardness and can effectively prevent curling, described transparent conductive laminate comprises described hard coating film, and described touch panel comprises described transparent conductive laminate.The 3rd hard conating that hard coating film of the present invention comprises transparent substrate layer, the first hard conating sequentially formed in the side, a face of this substrate layer and the second hard conating and formed in another side, face of substrate layer.The pencil hardness of the first hard conating is lower than the pencil hardness of described second hard conating, the pencil hardness of the second hard conating is more than 3H, the thickness of the first hard conating is 4 times ~ 20 times of the thickness of the second hard conating, the thickness of the second hard conating is 1 μm ~ 10 μm, and the thickness of the 3rd hard conating is 50nm ~ 10 μm.

Description

Hard coating film, transparent conductive laminate and touch panel
Technical field
The present invention relates to hard coating film, comprise the transparent conductive laminate of this hard coating film and comprise the touch panel of this transparent conductive laminate.
Background technology
LCD MODULE (LCD) has the features such as thin, lightweight, power consumption is little, described feature is utilized mostly LCD MODULE to be used as flat-panel monitor, and this purposes expands just year by year, can as information display devices such as mobile phone, personal digital assistant (PDA), PC, TVs.In recent years, according to purposes, be various to the characteristic required by LCD MODULE, as to the characteristic required by LCD MODULE, bright (high brightness) can be enumerated, easily see (wide viewing angle), energy-saving, slim lightweight and giant-screen etc.
In order to improve the ease for operation, swiftness etc. of the people of viewing, as described LCD MODULE, there is the LCD MODULE being provided with touch panel.In addition, the LCD MODULE being provided with touch panel has following structure usually: from face side to rear side, and overlap has touch panel, liquid crystal display cells, various optical sheet and backlight successively.
As described touch panel, there is the touch panel of capacitive way, resistive film mode and way of electromagnetic induction etc.As capacitive way, there is following mode: electrode is extended on cross one another direction, when finger waits contact touch panel, interelectrode electric capacity changes, and detects, detect input position thus to this capacitance variations; And to apply at the two ends of nesa coating that phase place is identical, alternating current that current potential is identical, when finger contact or near thus produce weak current when forming electric capacity, detect this weak current, detect input position thus; Etc..
In described LCD MODULE, in order to the resistance to impact and usability improving nesa coating and other optics can wait, mostly the surface of described optics is provided with hard coating film.As described hard coating film, there are known have the hard coating film of hard conating on the surface of substrate layer.As this hard coating film, patent document 1 discloses a kind of hard coating film, this hard coating film has double-deck hard conating: be provided with the first hard conating on the surface of substrate layer, is provided with the second hard conating (see No. 2000-71392, Japanese Laid-Open Patent Publication) on the surface of this first hard conating.Hard coating film described in this publication, the curing resin layer that formed by the mixture of free-radical polymerised resin and cationically polymerizable resin is provided with as the first hard conating on the surface of substrate layer, the second hard conating that thickness is substantially identical with the thickness of the first hard conating is provided with on the surface of this first hard conating, can marresistance be kept thus, and bending (カ ー Le can be prevented) and can crackle be prevented.
In addition, as the hard coating film with double-deck hard conating, patent document 2 discloses a kind of hard coating film, pencil hardness as the first hard conating of internal layer is lower than the pencil hardness as outer field second hard conating, and the thickness of Thickness Ratio second hard conating of the first hard conating is thick (see No. 2007-219013, Japanese Laid-Open Patent Publication).Hard coating film described in this publication is that therefore the thickness of the second hard conating is the about over half of the thickness of the first hard conating by stacked the first hard conating formed by the urethane acrylate etc. of lower shrinkage of identical coating process and the second hard conating formed by the urethane acrylate etc. of high rigidity.
But the hard coating film of described patent document 1, because the first hard conating is substantially identical with the thickness of the second hard conating, therefore the first hard conating is thin, and the surface of hard coating film cannot obtain enough hardness.In addition, if increase the thickness of hard conating to obtain enough hardness, then the second hard conating can become blocked up, there is this hard coating film and can produce curling problem.
In addition, the hard coating film of described patent document 2, although the thickness of Thickness Ratio first hard conating of the second hard conating is thinner, but the thickness of the second hard conating is the about over half of the thickness of the first hard conating, therefore as its result, the surface of hard coating film cannot obtain enough hardness, in addition, can not reliably prevent curling.
Prior art document
Patent document 1: No. 2000-71392, Japanese Laid-Open Patent Publication
Patent document 2: No. 2007-219013, Japanese Laid-Open Patent Publication
Summary of the invention
In view of described problem, the object of the present invention is to provide the hardness with excellence also effectively can prevent curling hard coating film, comprise the transparent conductive laminate of this hard coating film and comprise the touch panel of this transparent conductive laminate.
In order to solve described problem, the invention provides a kind of hard coating film, it comprises: transparent substrate layer, first hard conating, is formed at the side, a face of described substrate layer, second hard conating, is formed at the side, a face of described first hard conating, and the 3rd hard conating, be formed at another side, face of described substrate layer, the pencil hardness of described first hard conating is lower than the pencil hardness of described second hard conating, the pencil hardness of described second hard conating is more than 3H, the thickness of described first hard conating is more than 4 times less than 20 times of the thickness of described second hard conating, the thickness of described second hard conating is more than 1 μm less than 10 μm, the thickness of described 3rd hard conating is more than 50nm less than 10 μm, the main component of described first hard conating is uv curing resin, described first hard conating contains UV resistant agent and polymerization initiator, described UV resistant agent is below more than 0.1 quality % 10 quality % relative to the content of the main component of described first hard conating, described polymerization initiator is below more than 1 quality % 10 quality % relative to the content of the main component of described first hard conating.
This hard coating film, by the 3rd hard conating formed in another side, face of substrate layer, can improve the hardness of another side, face.Particularly this hard coating film is thinned to more than 50nm less than 10 μm by making the thickness of the 3rd hard conating be formed as, and can improve the hardness of another side, face of substrate layer, and the difference of hardness because of substrate layer and the 3rd hard conating can be prevented and cause produce curling.In addition, this hard coating film is configured with pencil hardness first hard conating lower than the pencil hardness of the second hard conating between substrate layer and the second hard conating.Therefore, this hard coating film can prevent the nonhomogeneous hardness because of substrate layer and the second hard conating and cause and produce curling, and by the first hard conating and the second hard conating, effectively can improve the hardness of the side, a face of this hard coating film.Particularly by making the thickness of the second hard conating in described scope, and the thickness of the first hard conating is remained in the scope of more than 4 times less than 20 times of the thickness of the second hard conating, thus this hard coating film the pencil hardness because of the second hard conating can be prevented well higher and cause produce curling.In addition, this hard coating film has above-mentioned formation because of the first hard conating, the second hard conating and the 3rd hard conating, so can improve the hardness of side, two sides and can improve usability etc., and can meet the requirement of slimming.
In described hard coating film, preferably, the pencil hardness of described first hard conating is more than F below H.Thus, the hardness of the side, a face of hard coating film can effectively be improved further.
In described hard coating film, preferably, the thickness of described first hard conating is more than 20 μm less than 100 μm.Thus, can prevent well further curling.
In described hard coating film, preferably, the pencil hardness of described substrate layer is more than 8B below F.The pencil hardness of the substrate layer of this hard coating film is when described scope, and this hard coating film can prevent curling, and can improve hardness well.
In described hard coating film, preferably, the main component of described substrate layer is polycarbonate resin, cycloolefin resinoid or PETG resinoid.Even if when this hard coating film uses the hardness such as polycarbonate resin, cycloolefin resinoid or PETG resinoid lower thus easily produces the main component of curling resin as substrate layer, also can prevent curling, and effectively can improve hardness.By using polycarbonate resin, cycloolefin resinoid or PETG resinoid as the main component of substrate layer, this hard coating film easily can reduce length of delay in face (Ro) and thickness direction retardation value (Rth).By adopting polycarbonate resin as the main component of described substrate layer, this hard coating film can improve resistance to impact.In addition, by adopting cycloolefin resinoid as the main component of described substrate layer, this hard coating film effectively can suppress the change of the phase difference produced because of external force such as direct sunlight and display heatings, can have excellent optical homogeneity, and can carry out meticulous image display.By adopting PETG resinoid as the main component of described substrate layer, this hard coating film more effectively can improve hardness.
In described hard coating film, preferably, in the face of described substrate layer, length of delay (Ro) is below 100nm, and the thickness direction retardation value (Rth) of described substrate layer is below 200nm.Thus, when by overlapping with other optics for described hard coating film use, the optical function damaging other optics can be prevented.
In described hard coating film, preferably, the main component of described first hard conating is uv curing resin.Thus, produceability can be improved.In addition, described hard coating film can prevent thermal expansion because substrate layer is produced by heating or thermal contraction, thus can improve dimensional stability.
In described hard coating film, when the main component as described first hard conating contains uv curing resin, preferably, described uv curing resin is cationically polymerizable resin.Thus, the cohesive of described first hard conating and substrate layer can be improved, and bonding force can be suppressed to change in time.In addition, by using cationically polymerizable resin as the main component of the first hard conating, described hard coating film can prevent curling, and can improve dimensional stability further.
In described hard coating film, preferably, described first hard conating contain uv curing resin as main component while, described first hard conating is also containing UV resistant agent.Usually, be uv curing resin in the main component of the first hard conating, and when also containing UV resistant agent in this first hard conating, the curing rate of this first hard conating is slack-off, and productivity ratio reduces.But it is thicker that the thickness due to the first hard conating of described hard coating film sets, though therefore when by the control of the concentration of UV resistant agent at low concentration, also can containing the UV resistant agent of q.s in the first hard conating.Therefore, even if when containing the anti-anti-outside line agent of q.s in the first hard conating, described hard coating film also can suppress the curing rate of the first hard conating to reduce, thus can prevent productivity ratio from reducing.
In described hard coating film, preferably, in described 3rd hard conating, dispersion contains high-refractive index particulate.Thus, the refractive index of the 3rd hard conating can be improved.
In described hard coating film, preferably, the refractive index of described 3rd hard conating is less than more than 1.6 2.3.Thus, when the 3rd hard conating side of described hard coating film is laminated in the transparency conducting layer of touch panel etc., the refractive index of the refractive index of the 3rd hard conating and transparency conducting layer can be made close, such as, the refractive index of the 3rd hard conating can be made close to the refractive index 2.1 ~ 2.2 (λ=520nm) of ITO.Its result, described hard coating film can reduce the observability of the electrode pattern being formed at transparency conducting layer.
In addition, in order to solve described problem, the present invention also provides a kind of transparent conductive laminate, and it comprises: described hard coating film; And transparency conducting layer, be laminated in another face of described 3rd hard conating.
This transparent conductive laminate, owing to comprising described hard coating film, therefore can prevent described hard coating film from producing curling well.In addition, this transparent conductive laminate, owing to comprising described hard coating film, so can improve the hardness of side, two sides and can improve usability, and can meet the requirement of slimming.In addition, in this transparent conductive laminate, close by the refractive index of the refractive index and transparency conducting layer that make the 3rd hard conating, thus when described transparent conductive laminate is such as touch panel, the observability of the electrode pattern being formed at transparency conducting layer can be reduced.
In described transparent conductive laminate, preferably, the difference of the described refractive index of the 3rd hard conating and the refractive index of described transparency conducting layer is less than 0.6.Thus, the observability of the electrode pattern being formed at transparency conducting layer can be reduced further.
In addition, in order to solve described problem, the present invention also provides a kind of touch panel, and it comprises described transparent conductive laminate.
This touch panel, owing to comprising described hard coating film, therefore can prevent described hard coating film from producing curling very well.In addition, this touch panel, owing to comprising described hard coating film, so can improve the hardness of side, two sides and can improve usability etc., and can meet the requirement of slimming.In addition, close by the refractive index of the refractive index and transparency conducting layer that make the 3rd hard conating, described touch panel can reduce the observability of the electrode pattern being formed at transparency conducting layer thus.
In addition, in the present invention, so-called " pencil hardness " refers to the numerical value that the Pencil scratch value recorded in the test method specified based on JISK5600-5-4 obtains.In the present invention, make the pencil hardness of the pencil hardness of the pencil hardness of the first hard conating, the second hard conating and the 3rd hard conating all high than the pencil hardness of substrate layer.So-called " thickness " refers to and measures according to JISK7130 the average thickness obtained." in face length of delay (Ro) " is the value obtained by Ro=(Ny-Nx) × d." thickness direction retardation value (Rth) " is the value obtained by Rth=((Nx+Ny)/2-Nz) × d.Wherein, Nx is the refractive index of the fast axle (axle parallel with direction, face) of film, Ny is the refractive index of the slow axis (parallel with direction, face and vertical with fast axle axle) of film, Nz is the refractive index of the film on thickness direction (direction vertical with direction, face), and d is the thickness of film.
So-called " UV resistant agent " refers to the additive with the function preventing the light deterioration caused because of ultraviolet, and the concept of " UV resistant agent " comprises ultra-violet absorber and ultra-violet stabilizer etc.
As mentioned above, hard coating film of the present invention, the transparent conductive laminate comprising this hard coating film and the touch panel comprising this transparent conductive laminate can improve the hardness of described hard coating film, and can effectively prevent curling.
Accompanying drawing explanation
Fig. 1 is the schematic sectional view of the hard coating film representing one embodiment of the present invention.
Fig. 2 represents the schematic sectional view with the hard coating film of the hard coating film different modes of Fig. 1.
Fig. 3 is the schematic sectional view of the transparent conductive laminate representing one embodiment of the present invention.
Fig. 4 is the schematic sectional view of the touch panel representing one embodiment of the present invention.
Fig. 5 represents the schematic sectional view with the touch panel of the touch panel different modes of Fig. 4.
Description of reference numerals
1 hard coating film
2 substrate layers
3 face side hard conatings
4 rear side hard conatings (the 3rd hard conating)
5 first hard conatings
6 second hard conatings
11 hard coating films
12 rear side hard conatings (the 3rd hard conating)
21 transparent conductive laminates
22 transparency conducting layers
31 touch panels
32 glass substrates
33 adhesive layers
41 touch panels
42 point-like septs
43 column spacers
44 transparency conducting layers
45 high refractive index layers
46 glass substrates
Detailed description of the invention
First embodiment
Referring to suitable accompanying drawing, embodiments of the present invention are described in detail.
The hard coating film 1 of Fig. 1 comprises substrate layer 2, face side hard conating 3 and rear side hard conating 4 (being equivalent to the 3rd hard conating).In addition, when this hard coating film 1 bonds with miscellaneous part, rear side hard conating 4 is configured at adhesive surface side, face side hard conating 3 is configured in the opposite side of adhesive surface.
Substrate layer 2
Substrate layer 2 is because need to make light therethrough, so be transparent, particularly water white.Although there is no particular limitation for the main component of formation substrate layer 2, be typically selected from the group be made up of polycarbonate resin, cycloolefin resinoid, acrylic resin, polypropylene-based resin and PETG resinoid.These synthetic resin have excellent optical transparence, can make light well through.Wherein, as the main component forming substrate layer 2, preferably polycarbonate resin, cycloolefin resinoid or PETG resinoid.
Only otherwise the infringement transparency and the intensity that requires, substrate layer 2 can also containing other any composition, the preferably main component that described synthetic resin be made up of of substrate layer 2 containing more than 90 quality %, the more preferably main component that described synthetic resin be made up of of substrate layer 2 containing more than 98 quality %.At this, as the example of any composition, UV resistant agent, lubricant, processing aid, plasticizer, shock-resistant auxiliary agent, phase difference depressant, delustering agent, antiseptic, mould inhibitor etc. can be enumerated.
As the polycarbonate resin forming substrate layer 2, there is no particular limitation, can be only Linear polycarbonate resinoid or branched polycarbonate resinoid any one, also can be the polycarbonate resin be made up of Linear polycarbonate resinoid and branched polycarbonate resinoid.
Linear polycarbonate resinoid is the linear aromatic polycarbonate resin manufactured by known phosgenation or fusion method, is made up of carbonate component and bis-phenol (ジ Off ェ ノ ー Le) composition.As the precursor for importing carbonate component, phosgene, diphenyl carbonate etc. can be exemplified.In addition, as bis-phenol, can 2 be exemplified, 2-bis-(4-hydroxy phenyl) propane, 2, 2-bis-(3, 5-dimethyl-4-hydroxy phenyl) propane, 1, 1-bis-(4-hydroxy phenyl) cyclohexane, 1, 1-bis-(3, 5-dimesyl-4-hydroxy phenyl) cyclohexane, 1, 1-bis-(4-hydroxy phenyl) decane, 1, 1-bis-(4-hydroxy phenyl) propane, 1, 1-bis-(4-hydroxy phenyl) cyclodecane, 1, 1-bis-(3, 5-dimethyl-4-hydroxy phenyl) cyclododecane, 4, 4 '-dihydroxy diphenyl ether, 4, 4 '-thiodiphenol, 4, 4 '-dihydroxy-3, 3-bis-ring diphenyl ether etc.These materials can be used alone, and also two or more combinations of substances can be used.Described Linear polycarbonate resinoid can be manufactured by the method etc. recorded in such as No. 3989672, US Patent No., its refractive index preferably less than more than 1.57 1.59.
As branched polycarbonate resinoid, be the polycarbonate resin using branching agent to manufacture, as branching agent, can phloroglucin be exemplified, trimellitic acid, 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,2-tri-(4-hydroxy phenyl) ethane, 1,1,2-tri-(4-hydroxy phenyl) propane, 1,1,1-tri-(4-hydroxy phenyl) methane, 1,1,1-tri-(4-hydroxy phenyl) propane, 1,1,1-tri-(2-methyl-4-hydroxy phenyl) methane, 1,1,1-tri-(2-methyl-4-hydroxy phenyl) ethane, 1,1,1-tri-(3-methyl-4-hydroxy phenyl) methane, 1,1,1-tri-(3-methyl-4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) methane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, 1,1,1-tri-(3-chloro-4-hydroxyl phenyl) methane, 1,1,1-tri-(3-chloro-4-hydroxyl phenyl) ethane, 1,1,1-tri-(the chloro-4-hydroxy phenyl of 3,5-bis-) methane, 1,1,1-tri-(the chloro-4-hydroxy phenyl of 3,5-bis-) ethane, 1,1,1-tri-(the bromo-4-hydroxy phenyl of 3-) methane, 1,1,1-tri-(the bromo-4-hydroxy phenyl of 3-) ethane, 1,1,1-tri-(the bromo-4-hydroxy phenyl of 3,5-bis-) methane, 1,1,1-tri-(the bromo-4-hydroxy phenyl of 3,5-bis-) ethane, 4,4 '-dihydroxy-2,5-dihydroxy diphenyl ether etc.
Such as, enumerate in as flat in Japanese Laid-Open Patent Publication No. 03-182524, described branched polycarbonate resinoid can prepare by the following method: stir the reaction mixture comprising polycarbonate oligomer, aromatic bisphenols class and the end-capping reagent obtained by aromatic bisphenols class, described branching agent photoreactive gas, while carry out stirring limit in the mode making described reaction mixture form turbulent flow to described reaction mixture, described material is reacted, when the viscosity of reaction mixture raises, add aqueous alkali and make reaction mixture form laminar flow and react.In polycarbonate resin, comprise the branched polycarbonate resinoid of the resin combination of the present invention of the following scope of more than 5 quality % 80 quality %, preferably comprise the scope of below more than 10 quality % 60 quality %.This be due to: when branched polycarbonate resinoid is less than 5 quality %, then have that tensile viscosity reduces, the problem of difficult forming in extrusion molding; When more than 80 quality %, then there is the problem that shear viscosity raises, molding processibility reduces of resin.
As the cycloolefin resinoid forming substrate layer 2, as long as have the resin of the monomeric unit be made up of cyclic olefin (cycloolefin), just there is no particular limitation.As the cycloolefin resinoid used in substrate layer 2, can be any one of cyclic olefin polymer (COP) or cyclic olefine copolymer (COC), preferably cyclic olefine copolymer.
Described cyclic olefine copolymer refers to the amorphism cyclic olefin resinoid of the copolymer as the alkene such as cyclic olefin and ethene.As cyclic olefin, there is the cyclic olefin of polycycle and the cyclic olefin of monocyclic.As the cyclic olefin of described polycycle, ENB, methyinorbornene, dimethyl ENB, ethyl norbornene, ENB, butyl ENB, bicyclopentadiene, dihydro bicyclopentadiene, methyl dicyclopentadiene, dimethyl bicyclopentadiene, tetracyclododecen, methyl tetracyclododecen, dimethyl tetracyclododecen, three cyclopentadiene, tetracyclopentadiene etc. can be enumerated.In addition, as the cyclic olefin of monocyclic, cyclobutane, cyclopentene, cyclo-octene, cyclo-octadiene, cyclo-octatriene, cyclodoecatriene etc. can be enumerated.
The acrylic resin forming substrate layer 2 is the resin of the skeleton had from acrylic or methacrylic acid.As the example of acrylic resin, there is no particular limitation, poly-(methyl) acrylate such as polymethyl methacrylate can be enumerated, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) acrylate-styrene copolymer, there is the polymer (such as methyl methacrylate-cyclohexyl methacrylate copolymer of alicyclic alkyl, methyl methacrylate-(methyl) acrylic acid norborny ester copolymer) etc.In described acrylic resin, preferably poly-(methyl) acrylic acid C1-C6 Arrcostab, more preferably the Tri-n-butyltin methacrylate resin such as poly-(methyl) methyl acrylate.
The polypropylene-based resin forming substrate layer 2 is the resin of the skeleton had from propylene.As the example of polypropylene-based resin, there is no particular limitation, can enumerate the homopolymers of propylene or propylene and be selected from the copolymer that ethene and carbon number are more than one the monomer in the alpha-olefin of 4 ~ 12.
The PETG resinoid forming substrate layer 2 is the polymer obtained by terephthalic acid (TPA) and glycol reaction.PETG resinoid can also comprise other comonomer, repetitive preferably more than the 80mol% of PETG.PETG such as can be prepared by following method: dimethyl terephthalate (DMT) and ethylene glycol are mixed in reactor, limit slowly raises internal temperature limit makes reactant carry out ester exchange reaction, then product is moved in polymer reactor, under high-temperature vacuum, carry out polymerisation, generate PETG thus.
As length of delay (Ro) in the face of substrate layer 2, although there is no particular limitation, preferably below 100nm.The higher limit of length of delay more preferably 50nm in the face of substrate layer 2, further preferably 15nm, particularly preferably is 5nm.In addition, as the thickness direction retardation value (Rth) of substrate layer 2, although there is no particular limitation, preferably below 200nm.The higher limit more preferably 100nm of the thickness direction retardation value of substrate layer 2, further preferably 30nm, particularly preferably is 10nm.By length of delay in reduction face (Ro) and thickness direction retardation value (Rth), described hard coating film 1 can suppress the change action of transmitted ray, when described hard coating film 1 is overlapped other optics enterprising enforcement used time, can prevent from counteracting the optical function of this other optics.
As the pencil hardness of substrate layer 2, although there is no particular limitation, such as, in order to improve the hardness after affix hard conating further, preferably the pencil hardness of substrate layer 2 is more high better, and the pencil hardness of substrate layer 2 can be more than 8B below F.Even if the pencil hardness of substrate layer 2 is the degree of described scope, described hard coating film 1 also can prevent curling, and effectively the pencil hardness of side, a face can be brought up to the degree of more than 2H below 6H.
As the thickness of substrate layer 2, there is no particular limitation, such as preferably more than 20 μm less than 200 μm.The higher limit of the thickness of substrate layer 2 more preferably 150 μm, particularly preferably is 100 μm.On the other hand, the lower limit of the thickness of substrate layer 2 more preferably 30 μm, particularly preferably is 50 μm.When the thickness of substrate layer 2 exceedes described higher limit, the speed of production line when manufacturing and productivity ratio can be caused to reduce, in addition, when described hard coating film 1 is for liquid crystal indicator, exist with to the opposing problem of the requirement of the slimming that liquid crystal indicator proposes.On the contrary, when the thickness of substrate layer 2 is less than described lower limit, there is intensity and less rigid, prevent the problems such as bending property reduction.
As substrate layer 2, usually use arithmetic mean surface roughness (Ra) be less than more than 0.02 0.06 substrate layer.In addition, in substrate layer 2, as required, unglazed process can be carried out.The arithmetic mean surface roughness (Ra) implementing the substrate layer 2 of unglazed process preferably less than more than 0.07 2, more preferably less than more than 0.1 1.By by the Roughness Surface on Control of substrate layer 2 in described scope, can prevent from producing damage in the process after former film manufactures, can treatability be improved.In addition, usually, when batching the former film produced, needing that embossing processing (annular knurl processing process) is carried out to the two ends on the width of film and preventing into block.When carried out annular knurl processing process on film, because the treatment sites at film two ends can not use, therefore this part must be discarded in severing.In addition, carrying out in taking-up activities to film, in order to prevent causing damage to film, sometimes being covered by diaphragm.But, by the arithmetic mean surface roughness of substrate layer 2 is controlled in prescribed limit as above, just block can be prevented into without the need to carrying out annular knurl processing process, therefore manufacturing process is simple, two end portions on the width of film also can use, and can carry out along its length batching and can not produce the fault of film.In addition, substrate layer 2, by having suitable surface roughness, sustains damage when can effectively suppress to batch, and without the need to covering as described above.
There is no particular limitation for the manufacture method of substrate layer 2, such as, the additives such as the tablet raw material of synthetic resin and plasticizer can be mixed according to current known mixed method, be pre-formed thermoplastic resin composition, then manufactures substrate layer 2.Such as by with after the mixer premixeds such as the U.S. resistance to mixer (omnimixer) of Australia, extruding mixing to obtaining mixture, described thermoplastic resin composition can be obtained thus.In this case, for extruding mixing mixing roll, there is no particular limitation, and such as single screw extrusion machine, twin-screw can be used to go out the current known mixing roll of extruder or the pressure kneader etc. such as machine.
As the forming method of substrate layer 2, the known methods such as solution casting method (solution casting method), extrusion by melting, rolling process, compression forming method can be exemplified.Wherein, preferably solution casting method (solution casting method), extrusion by melting.Now, can use and carry out in advance extruding mixing thermoplastic resin composition, also other additive such as synthetic resin and plasticizer can be dissolved in a solvent respectively, then they are formed uniform mixed solution, backward solution casting method (solution casting method) or the film molding procedure of extrusion by melting described mixed solution is provided.In addition, in order to the length of delay of the length of delay of substrate layer 2 and hard coating film 1 is controlled to be certain, such as, can cool it by keeping the chill roll of uniform temperature and endless belt to sandwich molten resin with arc-shaped in the width direction.
As the solvent used in solution casting method (solution casting method), the chlorine such as chloroform, carrene kind solvent can be exemplified; The aromatic series kind solvents such as toluene, dimethylbenzene, benzene and their mixed solvent; The alcohols solvents such as methyl alcohol, ethanol, isopropyl alcohol, n-butanol, 2-butanols; Methyl Cellosolve, ethyl Cellosolve, butyl Cellosolve, dimethyl formamide, methyl-sulfoxide, dioxanes, cyclohexanone, oxolane, acetone, MEK (MEK), ethyl acetate, diethyl ether etc.These solvents can only be used, or two or more may be used.As the device for carrying out solution casting method (solution casting method), drum-type casting machine, band casting machine, spin coater etc. can be exemplified.
As extrusion by melting, T modulus method, blowing etc. can be enumerated.Film forming temperature when melt extruding preferably more than 150 DEG C less than 350 DEG C, more preferably more than 200 DEG C less than 300 DEG C.When forming film by T modulus method, in the leading section of known single screw extrusion machine or double screw extruder, T mould can be installed, batch and be extruded into membranaceous film, obtain the film of roll thus.Now, by suitably adjusting the temperature of takers-in, the process that film is extended can be applied in extrusion direction, can uniaxial tension operation be carried out thus.In addition, by increasing the operation making film extend on the direction vertical with extruding direction, biaxial stretch-formed, the simultaneously operation such as biaxial stretch-formed can be increased successively.
Face side hard conating 3
Face side hard conating 3 comprises the first hard conating 5 and the second hard conating 6.As the thickness of face side hard conating 3, although there is no particular limitation, preferably more than 21 μm less than 105 μm.The higher limit of the thickness of face side hard conating 3 more preferably 82 μm, further preferably 63 μm.On the other hand, the lower limit of the thickness of face side hard conating 3 more preferably 32 μm, further preferably 43 μm.When the thickness of face side hard conating 3 exceedes described higher limit, substantially not quite can promote to prevent curling effect, and exist with to the opposing problem of the requirement of the slimming that described hard coating film 1 proposes.On the contrary, when the thickness of face side hard conating 3 is less than described lower limit, exists and can not effectively prevent curling problem.
First hard conating 5
First hard conating 5 is formed at a face of substrate layer 2.First hard conating 5 can only be formed by resin, also can containing additives such as UV resistant agents.As the main component of formation first hard conating 5, there is no particular limitation, the resin etc. that can exemplify active energy line curing resin or be formed by reactive silicon compound.As active energy line curing resin, uv curing resin, electronic beam curing resin, radiation-curable resin etc. can be enumerated.In addition, as reactive silicon compound, tetraethoxysilane etc. can be enumerated.Wherein, as the main component of the first hard conating 5, preferably uv curing resin.By using uv curing resin as the main component of the first hard conating 5, described hard coating film 1 can improve produceability.In addition, by using uv curing resin as the main component of the first hard conating 5, during fabrication etc., described hard coating film 1 can prevent the thermal expansion that produces owing to applying heat to substrate layer 2 or thermal contraction, thus can improve dimensional stability.As described uv curing resin, free-radical polymerised resin, cationically polymerizable resin etc. can be enumerated.
As forming the ultraviolet polymerizing compound of described uv curing resin, the monomer or oligomer that are solidified by reactions such as ultraviolet can carry out being polymerized, be cross-linked can be used.
As described monomer, free radical polymerization monomer, cationically polymerizable monomer etc. can be enumerated.In addition, as described oligomer, free-radical polymerised oligomer, cationically polymerizable oligomer etc. can be enumerated.
As described free radical polymerization monomer, simple function (methyl) esters of acrylic acids such as (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl ester can be exemplified; Various (methyl) acrylate such as multifunctional (methyl) esters of acrylic acid such as two (methyl) acrylic acid DPG ester, two (methyl) acrylic acid 1,6-hexylene glycol ester, two (methyl) acrylic acid DOPCP, three (methyl) acrylic acid trihydroxymethylpropanyl ester, three (methyl) acrylate, pentaerythritol, four (methyl) acrylate, pentaerythritol, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester.
As described cationically polymerizable monomer, can 3 be exemplified, 4-epoxy hexane ylmethyl-3 ', the oxetanes classes etc. such as the vinyl ethers such as glycidol ethers, 4-hydroxybutyl vinyl ether such as alicyclic epoxy thing class, the bisphenol A diglycidyl ethers such as 4 '-epoxy hexane yl carboxylic acid ester, 3-ethyl-3-hydroxymethyl oxetane.
As described free-radical polymerised oligomer, various (methyl) acrylate oligomers such as polyurethane (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, triazine (methyl) acrylate, silicon (methyl) acrylate can be exemplified; The polymercaptan quasi-oligomers such as trimethylolpropane tris mercaptoacetate, pentaerythrite four mercaptoacetate; Unsaturated polyester ester oligomer etc.
As described cationically polymerizable oligomer, can exemplified by novolak-type epoxy resin oligomer, aromatic ethenyl ether resin oligomer etc.
Wherein, as the ultraviolet polymerizing compound forming the uv curing resin being used for the first hard conating 5, preferably cationically polymerizable monomer or cationically polymerizable oligomer.
Described hard coating film 1 uses uv curing resin as the main component of the first hard conating 5, and by using cationically polymerizable monomer or cationically polymerizable oligomer as the ultraviolet polymerizing compound forming described uv curing resin, the cohesive of substrate layer 2 and the first hard conating 5 can be improved, and bonding force can be suppressed to change in time.In addition, according to described structure, described hard coating film 1 can prevent the first hard conating 5 cure shrinkage, thus can improve dimensional stability further.
In addition, as described cationically polymerizable monomer, preferably alicyclic epoxy thing class or oxetanes class.The polarity of described alicyclic epoxy thing class and oxetanes class is higher, and the glass transition temperature of the cationically polymerizable resin obtained by these polymerizable compounds is usually higher.Therefore, by using alicyclic epoxy thing class or oxetanes class as the cationically polymerizable monomer for the first hard conating 5, described hard coating film 1 can improve heat resistance.
As the glass transition temperature of described cationically polymerizable resin, although there is no particular limitation, preferably more than 180 DEG C, more preferably more than 200 DEG C, particularly preferably be more than 220 DEG C.By making the glass transition temperature of cationically polymerizable resin in described scope, described hard coat film 1 can significantly improve heat resistance.
In addition, according to required performance etc., can two or more used in combination by described monomer and oligomer.
In addition, as the ultraviolet polymerizing compound forming the uv curing resin being used for the first hard conating 5, also preferably the free-radical polymerised compound that cure shrinkage is low is used.As this free-radical polymerised compound, the polymethyl acryloxypropylethoxysilane silsesquioxane (Port リ メ タ Network リ ロ キ シ プ ロ ピ Le シ Le セ ス キ オ キ サ Application) that molecular weight is 1000 ~ 3000 can be exemplified.In addition, as the uv curing resin with described free-radical polymerised compound, the free-radical polymerised resin such as enumerated in No. 2008-120845, Japanese Laid-Open Patent Publication can also be used.
As polymerization initiator contained in the first hard conating 5, when ultraviolet polymerizing compound be free-radical polymerised monomer or oligomer, the compounds such as benzophenone, thioxanthene ketone, benzoin class, acetophenones can be enumerated.In addition, as polymerization initiator contained in the first hard conating 5, when ultraviolet polymerizing compound be cationically polymerizable monomer or oligomer, the compounds such as metallocene (メ タ ロ セ Application) class, aromatic matte class, aromatic series iodine class can be enumerated.
As the content of described polymerization initiator, there is no particular limitation, relative to uv curing resin, and preferably below more than 1 quality % 10 quality %, more preferably below more than 3 quality % 6 quality %.When the content of polymerization initiator exceedes described higher limit, the degree of polymerization of uv curing resin reduces, and there is the problem that can not obtain desired hardness.On the contrary, when the content of polymerization initiator is less than described lower limit, there is the problem that curing reaction can not fully carry out.
In addition, in order to improve coating, the first hard conating 5 can also contain solvent.As this solvent, the aliphatic hydrocarbon such as hexane, octane can be exemplified; The aromatic hydrocarbon such as toluene, dimethylbenzene; The alcohols such as ethanol, 1-propyl alcohol, isopropyl alcohol, n-butyl alcohol; The ketone such as MEK, methyl iso-butyl ketone (MIBK); The ester classes such as ethyl acetate, butyl acetate, isobutyl acetate; The glycol ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; The organic solvents such as the esterification such as ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate glycol ethers.These organic solvents can be used alone, as required, and also can by multiple used in combination.In addition, preferably, in the manufacturing process of the first hard conating 5, the evaporation of described solvent, drying is made.That is, the boiling point of described solvent is preferably in the scope of 60 ~ 160 DEG C.In addition, the saturated vapor of described solvent at 20 DEG C is pressed in the scope of 0.1 ~ 20kPa.For kind and the content of solvent, suitably can adjust according to the main component of the main component of substrate layer 2, the first hard conating 5 and thickness etc.
First hard conating 5 can also contain UV resistant agent.As UV resistant agent contained in the first hard conating 5, ultra-violet absorber, ultra-violet stabilizer etc. can be exemplified.
As described ultra-violet absorber, salicylic acid ultra-violet absorber, benzophenone ultraviolet absorbent, Benzotriazole Ultraviolet Stabilizer, cyanoacrylate ultraviolet absorbent, triazine-based ultraviolet absorbent, benzoxazine ketone ultra-violet absorber etc. can be exemplified, can use be selected from described ultra-violet absorber one or more.Wherein, from the view point of dispersiveness, preferably triazine-based ultraviolet absorbent, benzoxazine ketone ultra-violet absorber.In addition, as described ultra-violet absorber, the polymer with ultraviolet-absorbing group is preferably used in strand.By the polymer using this to have ultraviolet-absorbing group in strand, the deterioration of the ultraviolet radiation absorption function caused such as to ooze out due to ultra-violet absorber can be prevented.As described ultraviolet-absorbing group, BTA base, benzophenone base, alpha-cyanoacrylate ester group, triazine radical, salicyl, benzylidene malonic acid ester group etc. can be enumerated.Wherein, BTA base, benzophenone base, triazine radical particularly preferably is.
As described ultra-violet stabilizer, preferably use such as high to UV stable hindered amines ultra-violet stabilizer.By making the first hard conating 5 containing ultra-violet stabilizer, the inerting such as free radical, active oxygen because ultraviolet produces can be made, thus improve for ultraviolet stability, weatherability etc.In addition, if the first hard conating 5 is also with ultra-violet absorber and ultra-violet stabilizer, then can significantly improve for ultraviolet smooth deterioration preventing performance and weatherability.
As the content (mass ratio) of UV resistant agent relative to the main component of the first hard conating 5, although there is no particular limitation, preferably below more than 0.1 quality % 10 quality %.UV resistant agent is relative to the upper limit more preferably 8 quality % of the content of the main component of the first hard conating 5, further preferably 5 quality %.On the other hand, UV resistant agent is relative to the lower limit more preferably 1 quality % of the content of the main component of the first hard conating 5, further preferably 3 quality %.When the UV resistant agent of described hard coating film 1 exceedes the described upper limit relative to the content of the main component of the first hard conating 5, there is the problem that the durability of the first hard conating 5 etc. reduces.On the contrary, when the UV resistant agent of described hard coating film 1 is less than described lower limit relative to the content of the main component of the first hard conating 5, there is the problem that the first hard conating 5 can not realize anti-ultraviolet function effectively.
Preferably, the first hard conating 5 contains uv curing resin as main component to described hard coating film 1, and containing UV resistant agent.Usually, when the main component of the first hard conating 5 is uv curing resin and contains UV resistant agent in the first hard conating 5, the curing rate of the first hard conating 5 is slack-off, productivity ratio reduces.But, because the thickness of the first hard conating 5 by described hard coating film 1 is set to thicker, even if therefore by the concentration that the control of the concentration of UV resistant agent is less, the UV resistant agent containing q.s in the first hard conating 5 also can be made.Therefore, even if when containing the UV resistant agent of q.s in the first hard conating 5, described hard coating film 1 also can suppress the curing rate of the first hard conating 5 to reduce, thus can prevent productivity ratio from reducing.In addition, when the main component using polycarbonate resin as substrate layer 2, by making the first hard conating 5 containing UV resistant agent, described hard coating film 1 can prevent the xanthochromia etc. of substrate layer 2 effectively.
The pencil hardness of the first hard conating 5 is lower than the pencil hardness of the second hard conating 6.As the pencil hardness of the first hard conating 5, as long as lower than the pencil hardness of the second hard conating 6, just there is no particular limitation, preferably more than F below H.When the pencil hardness of the first hard conating 5 exceeds described higher limit, described hard coating film 1 becomes large because the difference of hardness of substrate layer 2 and the first hard conating 5 produces curling possibility.On the contrary, when the pencil hardness of the first hard conating 5 is less than described lower limit, there is the problem that described hard coating film 1 can not obtain desired hardness.
The thickness of the first hard conating 5 is more than 4 times less than 20 times of the thickness of the second hard conating 6.18 times of thickness of the upper limit of the thickness of the first hard conating 5 more preferably the second hard conating 6, further preferably 16 times.In addition, 6 times of thickness of the lower limit of the thickness of the first hard conating 5 more preferably the second hard conating 6, further preferably 8 times.When the thickness of the first hard conating 5 exceedes the described upper limit, exist and not quite can promote the problem preventing curling effect.On the contrary, when the thickness of the first hard conating 5 is less than described lower limit, exists and can not effectively prevent curling problem.
In addition, as the thickness of the first hard conating 5, although there is no particular limitation, preferably more than 20 μm less than 100 μm.The higher limit of the thickness of the first hard conating 5 more preferably 80 μm, further preferably 60 μm.On the other hand, the lower limit of the thickness of the first hard conating 5 more preferably 30 μm, further preferably 40 μm.When the thickness of the first hard conating 5 exceedes described higher limit, exist and not quite can promote the problem preventing curling action, also opposing with the requirement of the slimming proposed described hard coating film 1.On the contrary, when the thickness of the first hard conating 5 is less than described lower limit, exists and can not effectively prevent curling problem.
As the tensile elasticity rate of the first hard conating 5, although there is no particular limitation, preferably more than 1GPa below 4GPa.In addition, as the higher limit of the tensile elasticity rate of the first hard conating 5, more preferably 3.5GPa, further preferably 3GPa.On the other hand, as the lower limit of the tensile elasticity rate of the first hard conating 5, more preferably 1.5GPa, further preferably 2GPa.When the tensile elasticity rate of the first hard conating 5 exceedes described higher limit, exist and can not effectively prevent curling problem.On the contrary, when the tensile elasticity rate of the first hard conating 5 is less than described lower limit, there is the problem that described hard coating film 1 is difficult to the hardness desired by formation.In addition, " tensile elasticity rate " in the present invention measures according to JISK7113 the value obtained.
In addition, the value preferably 20kPamm cube that the tensile elasticity rate of the first hard conating 5 is multiplied by thickness obtained 3above 500kPamm 3below, more preferably 40kPamm 3above 400kPamm 3below, further preferably 60kPamm 3above 300kPamm 3below.When the value that the cube that the tensile elasticity rate of the first hard conating 5 is multiplied by thickness obtains exceeds described higher limit, the rigidity of the first hard conating 5 becomes excessive, exists and is difficult to problem hard coating film 1 being remained roll.On the contrary, when the value that the cube that the tensile elasticity rate of the first hard conating 5 is multiplied by thickness obtains is less than described lower limit, there is the first hard conating 5 and to be easily out of shape and the stress be applied on substrate layer 2 can become excessive problem.
As the arithmetic average roughness (Ra) on the surface of the side, a face of the first hard conating 5, although there is no particular limitation, preferably more than 0.5 μm less than 8 μm.The higher limit of the arithmetic average roughness (Ra) on the surface of the side, a face of the first hard conating 5 more preferably 7 μm, further preferably 6 μm.On the other hand, the lower limit of the arithmetic average roughness (Ra) on the surface of the side, a face of the first hard conating 5 more preferably 1 μm, particularly preferably is 2 μm.When the arithmetic average roughness (Ra) on the surface of the side, a face of the first hard conating 5 exceedes described higher limit, have the problem that the thickness of the second hard conating 6 formed in the side, a face of the first hard conating 5 can be made thickening.On the contrary, when the arithmetic average roughness (Ra) on the surface of the side, a face of the first hard conating 5 is less than described lower limit, the surface area of the side, a face of the first hard conating 5 can not be made to increase fully, the problem that the cohesive that therefore there is the first hard conating 5 and the second hard conating 6 reduces.On the other hand, when the arithmetic average roughness (Ra) of a face side surface of the first hard conating 5 is in described scope, the thickness of the second hard conating 6 can be made to remain suitable thickness, and effectively can improve the cohesive of the first hard conating 5 and the second hard conating 6.
In addition, as 10 mean roughness (Rz) on the surface of the side, a face of the first hard conating 5, although there is no particular limitation, preferably more than 0.5 μm less than 10 μm.The higher limit of 10 mean roughness (Rz) on the surface of the side, a face of the first hard conating 5 more preferably 9 μm, further preferably 8 μm.On the other hand, the lower limit of 10 mean roughness (Rz) on the surface of the side, a face of the first hard conating 5 more preferably 1 μm, further preferably 2 μm.When 10 mean roughness (Rz) on the surface of the side, a face of the first hard conating 5 exceed the described upper limit, exist and make the thickening possibility of the thickness of the second hard conating 6 can become large problem.On the contrary, when 10 mean roughness (Rz) on the surface of the side, a face of the first hard conating 5 are less than described lower limit, the surface area of the side, a face of the first hard conating 5 can not increase fully, the problem that the cohesive that therefore there is the first hard conating 5 and the second hard conating 6 reduces.In addition, " arithmetic average roughness (Ra) " and " 10 mean roughness (Rz) " is the value obtained according to JISB0601-2001.
There is no particular limitation for the manufacture method of the first hard conating 5, by coat activated energy line curing resin on a face of substrate layer 2, can make resin drying, irradiate active energy ray and manufacture the first hard conating 5.As the coating process of active energy line curing resin, as long as can on of substrate layer 2 face method of even spread active energy line curing resin, just there is no particular limitation, can enumerate the various method such as method of spin coating, spraying process, slope stream rubbing method, infusion process, stick coating method, rolling method, silk screen print method.In addition, in the manufacture of the first hard conating 5, as required, as pre-treatment, the surface modification treatment such as plasma treatment can be carried out under the inertness such as argon gas or nitrogen atmosphere.In addition, can also on the surface of substrate layer 2 stacked priming coat, by stacked first hard conating 5 of this priming coat.
Second hard conating 6
Second hard conating 6 is formed on a face of the first hard conating 5.As the material of formation second hard conating 6, there is no particular limitation.Second hard conating 6 can only be formed by resin, also can wherein containing additives such as silicon dioxide microparticles.
As the resin of formation second hard conating 6, thermosetting resin, active energy line curing resin etc. can be exemplified.
Such as can comprise the polymerizable monomer of active energy line curing resin or the coating composition of polyreactive oligomers by coating on a face of the first hard conating 5, make polymerizable monomer or polyreactive oligomers generation cross-linking reaction and/or polymerisation, form the second hard conating 6 thus.
As the polymerizable monomer of described active energy ray-curable or the functional group of polyreactive oligomers, preferably the functional group of ultraviolet, electron beam or radioactive ray polymerism, particularly preferably is ultraviolet polymerizing functional group.As ultraviolet polymerizing functional group, the unsaturated polymerizable functional group of ethene etc. such as (methyl) acryloyl group, vinyl, styryl, pi-allyl can be enumerated.
As described coating composition, although there is no particular limitation, preferably using acrylic monomer or urethane acrylate oligomer as the coating composition of main component.By forming the second hard conating 6 from the composition being main component with described monomer or oligomer, the hardness of the second hard conating 6 can be improved.Wherein, particularly preferably be from forming the second hard conating 6 containing urethane acrylate and the composition of (methyl) acrylic compounds simultaneously.
As the urethane acrylate of formation second hard conating 6 and the total content of (methyl) acrylic compounds, preferably below more than 45 quality % 99 quality %, further preferably below more than 50 quality % 95 quality %, particularly preferably is below more than 60 quality % 90 quality %.Form the urethane acrylate of the second hard conating 6 and (methyl) if the total content of acrylic compounds exceedes the described upper limit, then there is photopolymerisable beginning can the slack-off thus problem causing productivity ratio to reduce.In addition, form the urethane acrylate of the second hard conating 6 and (methyl) if the total content of acrylic compounds is less than described lower limit, then there is the problem that flexibility, mar proof, marresistance etc. reduce.On the other hand, form the urethane acrylate of the second hard conating 6 and (methyl) if the total content of acrylic compounds is in described scope, then can boost productivity, and suitable flexibility, mar proof and marresistance etc. can be kept well.
As described urethane acrylate, there is no particular limitation, can be monomer or oligomer any one.In addition, as the quantity of the functional group of urethane acrylate, there is no particular limitation, can be simple function group or polyfunctional group, preferably below more than 2 functional groups 6 functional groups, further preferably below more than 2 functional groups 3 functional groups.By making the functional group number of urethane acrylate in described scope, the hardness of the second hard conating 6 and the balance of percentage elongation can be kept well.Urethane acrylate can be used alone, and also can be used in combination of two or more.
As the glass transition temperature of the resin formed by urethane acrylate, although there is no particular limitation, preferably more than 40 DEG C less than 100 DEG C, further preferably more than 40 DEG C less than 80 DEG C.By making the glass transition temperature of the resin formed by urethane acrylate in described scope, hardness and the durability of the second hard conating 6 under normal temperature can be improved.
As the content of the urethane acrylate of formation second hard conating 6, although there is no particular limitation, but preferably below more than 10 quality % 90 quality %, further preferably below more than 15 quality % 85 quality %, particularly preferably be below more than 20 quality % 80 quality %.If the content forming the urethane acrylate of the second hard conating 6 exceedes the described upper limit, then there is the problem of mar proof and hardness of film reduction.In addition, if the content forming the urethane acrylate of the second hard conating 6 is less than described lower limit, then flexibility reduces, and the possibility cracked raises.On the other hand, if the content of the urethane acrylate of formation the second hard conating 6 is in described scope, then can keep suitable mar proof and hardness of film well, and suitable flexibility can be kept and can suppress to crack.
As described (methyl) acrylic compounds, there is no particular limitation, can be monomer or oligomer any one.As the quantity of the functional group of described (methyl) acrylic compounds, there is no particular limitation, can be simple function group or polyfunctional group.In addition, the second hard conating 6, by using (methyl) acrylic compounds with more than 3 functional groups, can improve durability.In addition, described (methyl) acrylic compounds can be the molecular structure with polar group, also can be the molecular structure of low polarity.(methyl) acrylic compounds can be used alone, and also can be used in combination of two or more.
As the polar group of (methyl) acrylic compounds, hydroxyl, carboxyl, amino, amide groups etc. can be enumerated.
As (methyl) acrylic compounds containing hydroxyl, (methyl) acrylic acid 2-hydroxyl ethyl ester can be exemplified, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 2-hydroxyl-3-phenoxy-propyl, 2-(methyl) acryloyl-oxyethyl-2-hydroxypropyl phthalate, glycerine list (methyl) acrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxybutyl, the acrylic acid ester etc. containing hydroxyl of (methyl) acrylic acid 4-hydroxybutyl etc. (methyl).
As (methyl) acrylic compounds containing carboxyl, except the ethene unsaturated carboxylic acids such as such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, 2-(methyl) acryloyloxyethyl succinate, 2-(methyl) acryloyl-oxyethyl phthalic acid ester, 2-(methyl) acryloyl-oxyethyl six hydrogen terephthalate etc. can also be enumerated.
As containing amino (methyl) acrylic compounds, (methyl) acrylic acid alkyl monosubstituted amino esters etc. such as (methyl) acrylic acid monomethylaminoethylester, (methyl) acrylic acid list ethylamino ethyl ester, (methyl) acrylic acid mono-methyl amino propyl ester, (methyl) acrylic acid list ethylamino propyl ester can be exemplified.
As (methyl) acrylic compounds containing amide groups, the acrylic amides etc. such as (methyl) acrylamide, N-methyl (methyl) acrylamide, N-methylol (methyl) acrylamide can be exemplified.
In addition, as (methyl) acrylic compounds of low polar molecular structure, (methyl) acrylate ring type ester or (methyl) alkyl acrylate can be exemplified.
As described (methyl) acrylate ring type ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid bicyclopentadiene ester, (methyl) acrylic acid tricyclodecenyl esters, (methyl) acrylic acid ENB ester etc. can be exemplified.
As described (methyl) alkyl acrylate, (methyl) lauryl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) benzyl acrylate, (methyl) octadecyl acrylate, (methyl) butyl acrylate, acrylic acid 1,6-hexylene glycol ester can be exemplified.
As (methyl) of formation second hard conating 6 although there is no particular limitation for the content of acrylic compounds, but preferably below more than 5 quality % 85 quality %, further preferably below more than 10 quality % 80 quality %, particularly preferably is below more than 15 quality % 75 quality %.Form (methyl) of the second hard conating 6 if the content of acrylic compounds exceedes the described upper limit, then the possibility cracked when shaping increases.In addition, form (methyl) of the second hard conating 6 if the content of acrylic compounds is less than described lower limit, then there is the problem of mar proof and hardness of film reduction.On the other hand, form (methyl) of the second hard conating 6 if the content of acrylic compounds is in described scope, then can keep suitable mar proof and hardness of film well, and suitable flexibility can be kept and can suppress to crack.
As described polymerization initiator, benzophenone can be exemplified, benzil, tetramethyl michaelis ketone, CTX, 2, 4-diethyl thioxanthone, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, 2, 2-diethoxy acetophenone, benzoin dimethylether, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropanone-1, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, two (cyclopentadienyl group)-two (2, the fluoro-3-of 6-bis-(pyrroles-1-base) titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1, 2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide etc.In addition, described compound can be used alone, also can by multiple used in combination.
The pencil hardness of the second hard conating 6 is more than 3H.Pencil hardness more preferably more than the 4H of the second hard conating 6, further preferably more than 5H.When the pencil hardness of the second hard conating 6 is less than described lower limit, exists and be difficult to make described hard coating film 1 form the problem of desired hardness.
The thickness of the second hard conating 6 is more than 1 μm less than 10 μm.The higher limit of the thickness of the second hard conating 6 more preferably 8 μm, further preferably 6 μm.On the other hand, the lower limit of the thickness of the second hard conating 6 more preferably 2 μm, further preferably 3 μm.When the thickness of the second hard conating 6 exceedes the described upper limit, can not effectively prevent curling, also opposing with the requirement of the slimming proposed described hard coating film 1 in addition.On the contrary, when the thickness of the second hard conating 6 is less than described lower limit, exists and be difficult to make described hard coating film 1 form the problem of desired hardness.
As the tensile elasticity rate of the second hard conating 6, although there is no particular limitation, preferably more than 1.5GPa below 6GPa.In addition the higher limit more preferably 5.5GPa of the tensile elasticity rate of described second hard conating 6, further preferably 5GPa.On the other hand, the lower limit more preferably 2GPa of the tensile elasticity rate of the second hard conating 6, further preferably 2.5GPa.When the tensile elasticity rate of the second hard conating 6 exceedes the described upper limit, exist and be difficult to effectively prevent curling problem.On the contrary, when the tensile elasticity rate of the second hard conating 6 is less than described lower limit, exists and be difficult to make described hard coating film 1 form the problem of desired hardness.
In addition, as the tensile elasticity rate of the second hard conating 6 and the ratio of the tensile elasticity rate of the first hard conating 5, although there is no particular limitation, preferably less than more than 1.5 4.The tensile elasticity rate of the second hard conating 6 and the upper limit of the ratio of the tensile elasticity rate of the first hard conating 5 more preferably 3.5, further preferably 3.On the other hand, the tensile elasticity rate of the second hard conating 6 and the lower limit of the ratio of the tensile elasticity rate of the first hard conating 5 more preferably 1.7, further preferably 2.When the tensile elasticity rate of the second hard conating 6 exceedes the described upper limit with the ratio of the tensile elasticity rate of the first hard conating 5, exist and be difficult to effectively prevent curling problem.On the contrary, when the tensile elasticity rate of the second hard conating 6 is less than described lower limit with the ratio of the tensile elasticity rate of the first hard conating 5, there is the problem that effectively can not improve the hardness of described hard conating 1.
There is no particular limitation for the manufacture method of the second hard conating 6, can be manufactured by the method identical with the manufacture method of the first hard conating 5.
Rear side hard conating 4
Rear side hard conating 4 is formed at another face of substrate layer 2.Form the main component of rear side hard conating 4 and the identical of the first hard conating 5.In addition, identical also with the first hard conating 5 of additive in rear side hard conating 4 is contained in.
As the pencil hardness of rear side hard conating 4, there is no particular limitation.In addition, the thickness as rear side hard conating 4 adopts more than 50nm less than 10 μm.The higher limit of the thickness of rear side hard conating 4 more preferably 7 μm, further preferably 5 μm.On the other hand, the lower limit more preferably 100nm of the thickness of rear side hard conating 4, further preferably 200nm.When the thickness of side hard conating 4 exceedes described higher limit overleaf, there is the problem curling possibility occurring and can increase, and also opposing with the requirement of the slimming proposed described hard coating film 1.On the contrary, when the thickness of side hard conating 4 is less than described lower limit overleaf, there is the problem that can not realize desired hardness.On the other hand, the thickness of side hard conating 4 is in described scope overleaf, hardness can be improved well, and can prevent curling and the slimming of described hard coating film 1 can be promoted.
There is no particular limitation for the manufacture method of rear side hard conating 4, can adopt the method identical with the manufacture method of the first hard conating 5.
Hard coating film 1
As the mist degree of described hard coating film 1, although there is no particular limitation, preferably less than 2%, more preferably less than 1%, further preferably less than 0.5%.When the mist degree of described hard coating film 1 exceedes described higher limit, the observability that there is image declines and the problem of the definition decline of shown image.
As the luminous ray transmissivity of described hard coating film 1, although there is no particular limitation, preferably more than 87%, further preferably more than 90%.When the luminous ray transmissivity of described hard coating film 1 is less than the lower limit of described scope, existence can not make light fully through, thus the problem causing observability to decline.
Described hard coating film 1, by being formed at the rear side hard conating 4 of another side, face of substrate layer 2, can improve the hardness of another side, face.Particularly by making the thickness of rear side hard conating 4 be thinned to described scope, described hard coating film 1 can improve the hardness of another side, face, and can prevent from causing because of substrate layer 2 and the difference of hardness of rear side hard conating 4 produce curling.In addition, between the substrate layer 2 and the second hard conating 6 of described hard coating film 1, the first hard conating 5 that pencil hardness is lower than the pencil hardness of the second hard conating 6 is provided with.Therefore, described hard coating film 1 can prevent from the difference of hardness because of substrate layer 2 and the second hard conating 6 from causing producing curling, and by the first hard conating 5 and the second hard conating 6, effectively can improve the hardness of the side, a face of described hard coating film 1.Particularly the first hard conating 5 of described hard coating film 1 is thicker.Therefore, hard coating film 1, by the first hard conating 5, effectively can realize for preventing curling pooling feature, and can improve the hardness of the side, a face of described hard coating film 1 well.Its result, even if the second hard conating 6 formation of described hard coating film 1 is thinner, by complementing each other with the first thicker hard conating 5 formed, also can make described hard coating film 1 obtain desired hardness.In addition, because the first hard conating 5, second hard conating 6 and rear side hard conating 4 have described formation, so described hard coating film 1 can improve the hardness of side, two sides, and can usability etc. be improved, and the requirement of slimming can be met.
Even if when the main component of the resin using lower, the easy generation of hardness such as polycarbonate resin, cycloolefin resinoid or PETG resinoid curling as the substrate layer 2 of described hard coating film 1, described hard coating film 1 also can prevent curling, and effectively can improve hardness.By using polycarbonate resin, cycloolefin resinoid or PETG resinoid as the main component of substrate layer 2, described hard coating film 1 easily can reduce length of delay in face (Ro) and thickness direction retardation value (Rth).By using polycarbonate resin as the main component of substrate layer 2, described hard coating film 1 can improve resistance to impact.In addition, by using cycloolefin resinoid as the main component of substrate layer 2, described hard coating film 1 can suppress the change of the phasic difference produced because of the external force such as heating of direct sunlight or display effectively, and can have excellent optical homogeneity, and can show meticulous image.By using PETG resinoid as the main component of substrate layer 2, described hard coating film 1 more effectively can improve hardness.
Second embodiment
Hard coating film 11
The hard coating film 11 of Fig. 2 comprises substrate layer 2, face side hard conating 3, rear side hard conating 12 (being equivalent to the 3rd hard conating).Substrate layer 2 in present embodiment is identical with face side hard conating 3 due to the substrate layer 2 of the hard coating film 1 with Fig. 1 with face side hard conating 3, therefore imparts identical Reference numeral to them, and eliminates their description.
Rear side hard conating 12
Rear side hard conating 12 is formed at another face of substrate layer 2.Form the main component (adhesive) of rear side hard conating 12, the additive be contained in rear side hard conating 12, the pencil hardness of rear side hard conating 12 and thickness, identical all with rear side hard conating 4.
In rear side hard conating 12, dispersion is containing high-refractive index particulate.As the described high-refractive index particulate disperseing in rear side hard conating 12 to contain, ZnO, TiO can be exemplified 2, CeO 2, SnO 2, ITO, Cs 0.33wO 3, Al 2o 3, La 2o 3, ZrO 2, Y 2o 3etc. inorganic material.
As the average grain diameter of described high-refractive index particulate, although there is no particular limitation, preferably more than 1nm below 100nm.The higher limit more preferably 80nm of the average grain diameter of described high-refractive index particulate, further preferably 60nm.On the other hand, the lower limit more preferably 5nm of the average grain diameter of described high-refractive index particulate, further preferably 10nm.When the average grain diameter of described high-refractive index particulate exceedes described higher limit, the problem that the transparency that there is rear side hard conating 12 reduces.On the contrary, when the average grain diameter of described high-refractive index particulate is less than described lower limit, the problem that the dispersiveness that there is high-refractive index particulate reduces.
As the manufacture method of rear side hard conating 12, such as described high-refractive index particulate can be dispersed in adhesive resin, after solvent dilution, utilize the known coating processes such as rolling method, method of spin coating, dip coating, spraying process, stick coating method, knife coating, die coating methods, ink jet type rubbing method, gravure coat method, form described rear side hard conating 12.
As the content of described high-refractive index particulate relative to adhesive, although there is no particular limitation, such as, can be below more than 10 quality % 60 quality %.
As the refractive index of rear side hard conating 12, although there is no particular limitation, preferably less than more than 1.6 2.3.The higher limit of the refractive index of rear side hard conating 12 more preferably 2.25, further preferably 2.2.On the other hand, the lower limit of the refractive index of rear side hard conating 12 more preferably 1.7, further preferably 1.75.The refractive index of side hard conating 12 is not in described scope overleaf, by time stacked to the rear side hard conating 12 of described hard coating film 11 and the transparency conducting layer of touch panel etc., the difference of the refractive index of rear side hard conating 12 and the refractive index of transparency conducting layer becomes greatly, the problem that the observability that existence is formed at the electrode pattern of transparency conducting layer can increase.
Described hard coating film 11 contains high-refractive index particulate due to dispersion in rear side hard conating 12, therefore can improve the refractive index of rear side hard conating 12.In addition, mist degree and the luminous ray transmissivity of described hard coating film 11 and the identical of hard coating film 1.
3rd embodiment
Transparent conductive laminate 21
The transparent conductive laminate 21 of Fig. 3 comprises hard coating film 11 and transparency conducting layer 22.Hard coating film 11 in present embodiment, due to identical with the hard coating film 11 of Fig. 2, therefore to which imparts identical Reference numeral, and eliminates its description.
Transparency conducting layer 22
Transparency conducting layer 22 is laminated in another face of rear side hard conating 12.As the formation material of transparency conducting layer 22, as long as have the conductive material of the transparency and electric conductivity, just there is no particular limitation, can enumerate mineral-type metal and organic conductive macromolecule.As mineral-type metal, gold, silver, copper, platinum, nickel, tin oxide, tin indium oxide (ITO) etc. can be exemplified.As organic conductive macromolecule, the organic conductive composition employing polyaniline, polythiophene, polypyrrole, polyquinoxaline etc. can be exemplified.Wherein, the ITO that preferably optical characteristics, outward appearance and electric conductivity are good or polythiophene class material.
As method side hard conating 12 being overleaf coated with the formation material of transparency conducting layer 22, there is no particular limitation, can adopt the known coating processes such as such as rolling method, method of spin coating, dip coating, spraying process, stick coating method, knife coating, die coating methods, ink jet type rubbing method, gravure coat method.In addition, when being coated with the formation material of transparency conducting layer 22, in order to improve the adhesion with rear side hard conating 12, also the pre-treatments such as Corona discharge Treatment can be carried out to rear side hard conating 12 in advance.
Form the curing of material as transparency conducting layer 22, can be cured by such as high-pressure mercury-vapor lamp, Halogen lamp LED, xenon lamp, nitrogen lasers, electron beam accelerator, radioactive element isoreactivity energy line source etc.In addition, as the exposure of active energy ray, with the accumulative quantometer under ultraviolet wavelength 365nm, preferably 50mJ/cm 2above 5000mJ/cm 2below.When exposure exceedes described higher limit, existence can cause the problem of active energy ray-curable coloring resin.On the contrary, when exposure is less than described lower limit, there is the problem that solidification is not enough.
In addition, also transparency conducting layer 22 can be formed by dry method such as sputtering methods.As the formation method of transparency conducting layer 22, from the view point of adhesion and slimming with rear side hard conating 12, form the method for transparency conducting layer 22 preferably by sputtering method.
As the thickness of the transparency conducting layer 22 when being formed by described sputtering method, although there is no particular limitation, preferably above below.The higher limit of transparency conducting layer 22 thickness when being formed by described sputtering method more preferably further preferably on the other hand, by described spatter method formed time transparency conducting layer 22 thickness lower limit more preferably further preferably when the thickness of transparency conducting layer 22 is in described scope, the performance of electric conductivity and these both sides of the transparency can be kept well.In addition, even if when the thickness of hard coating film 11 is thicker, by making the thickness of transparency conducting layer 22 in described scope, the slimming of described transparent conductive laminate 21 can also be promoted.
Described transparent conductive laminate 21, owing to comprising hard coating film 11, therefore can prevent hard coating film 11 from producing curling well.In addition, described transparent conductive laminate 21, owing to comprising hard coating film 11, so effectively can improve the hardness of the side, two sides of hard coating film 11, and can improve usability, and can meet the requirement of slimming.In addition, by making the refractive index of the refractive index of rear side hard conating 12 and transparency conducting layer 22 close, when described transparent conductive laminate 21 is such as touch panel, the observability of the electrode pattern being formed at transparency conducting layer 22 can be reduced.
As the difference of the refractive index of rear side hard conating 12 and the refractive index of transparency conducting layer 22, although there is no particular limitation, preferably less than 0.6, more preferably less than 0.5, further preferably less than 0.3.By making the difference of the refractive index of the refractive index of rear side hard conating 12 and transparency conducting layer 22 in described scope, thus described transparent conductive laminate 21 can reduce the observability of the electrode pattern being formed at transparency conducting layer 22 further.
4th embodiment
Touch panel 31
The touch panel 31 of Fig. 4 is the touch panel of capacitive way.Touch panel 31 comprises transparent conductive laminate 21, glass substrate 32 and adhesive layer 33.Transparent conductive laminate 21 in present embodiment, due to identical with the transparent conductive laminate 21 of Fig. 3, therefore to which imparts identical Reference numeral, and eliminates its description.
Transparent conductive laminate 21 is layered on glass substrate 32 by adhesive layer 33.As adhesive layer 33, there is no particular limitation, can enumerate the adhesive layer employing the known resin of binding property such as acrylic resin, polyurethane based resin.The mode of the face side (the people side of viewing) of transparency conducting layer 22 is positioned to configure touch panel 31 to make hard coating film 11.
Described touch panel 31, owing to comprising hard coating film 11, therefore can prevent hard coating film 11 from producing curling well.In addition described touch panel 31 is owing to comprising hard coating film 11, therefore can improve the hardness of the side, two sides of hard coating film 11 and can improve usability, and can meet the requirement of slimming.In addition, close by the refractive index of the refractive index and transparency conducting layer 22 that make the rear side hard conating 12 of described touch panel 31, described touch panel 31 can reduce the observability of the electrode pattern being formed at transparency conducting layer 22.
5th embodiment
Touch panel 41
The touch panel 41 of Fig. 5 is the touch panel of resistive film mode.Touch panel 41 comprises transparent conductive laminate 21, multiple point-like sept 42, column spacer 43, transparency conducting layer 44, high refractive index layer 45 and glass substrate 46.The mode of the face side of transparency conducting layer 22 is positioned to configure touch panel 41 to make hard coating film 11.
Multiple point-like septs 42 are formed at the surface of transparency conducting layer 44.As the formation material of point-like sept 42, the insulating resin such as epoxy resin or silicones can be exemplified.Column spacer 43 is arranged between transparency conducting layer 22 and transparency conducting layer 44.As the formation material of column spacer 43, the insulating resins such as epoxy resin, polyester, acrylic resin can be exemplified.Column spacer 43 is fixed on the edge part of the rear side of transparency conducting layer 22 and is fixed on the edge part of the face side of transparency conducting layer 44.Column spacer 43 is configured to transparency conducting layer 22 and transparency conducting layer 44 are separated from each other.Transparency conducting layer 44 is laminated in the surface of high refractive index layer 45 by the method identical with transparency conducting layer 22.As the formation material of transparency conducting layer 44, there is no particular limitation, can enumerate the formation material identical with the formation material of transparency conducting layer 22.High refractive index layer 45 is laminated in the surface of glass substrate 46.As the formation material of high refractive index layer 45, there is no particular limitation, can enumerate the formation material identical with the formation material of rear side hard conating 12.As the laminating method of high refractive index layer 45, there is no particular limitation, such as, can pass through the surface that adhesive layer (not shown) is laminated in glass substrate 46.
Described touch panel 41 is owing to comprising hard coating film 11, so it is curling to prevent hard coating film 11 from producing well.In addition described touch panel 41 is owing to comprising hard coating film 11, so can improve the hardness of the side, two sides of hard coating film 11 and can improve usability, and can meet the requirement of slimming.In addition, by making the refractive index of the refractive index of rear side hard conating 12 and transparency conducting layer 22 close, touch panel 41 can reduce the observability of the electrode pattern being formed at transparency conducting layer 22.Other embodiment
In addition, hard coating film of the present invention, comprise the transparent conductive laminate of this hard coating film and comprise the touch panel of this transparent conductive laminate, except described mode, also can implement in the mode of various distortion, improvement.Such as, described hard coating film also can be formed with adhesive layer in another side, face.As this adhesive layer, the adhesive layer employing the known resin of binding property such as acrylic resin, polyurethane based resin can be enumerated.Can by substrate layer or high refractive index layer another side, face coat binding agent solution and make its drying form described adhesive layer.In addition, also by coat binding agent solution make it dry on a face of release liners in advance, then the release liners and the 3rd hard conating with adhesive can be fitted, form adhesive layer thus.
Replace dispersion in the 3rd hard conating of described hard coating film to contain high-refractive index particulate, described hard coating film also can be that in the 3rd hard conating, dispersion contains high-refractive index particulate and contains the higher synthetic resin of refractive index ratio as main component.As such synthetic resin, phenolic resins, melmac, polyurethane resin, urea resin, diallyl phthalate resin, guanamine resin, unsaturated polyester resin, amino-alkyd resin, melamine-urea cocondensation resin, silicones, polyorganosiloxane resin etc. can be exemplified.Described hard coating film also can on the second hard conating other layer stacked (such as UV absorbed layer, antistatic layer and anti-reflection layer etc.).Described hard coating film also can have intermediate layer between substrate layer and the first hard conating, between the first hard conating and the second hard conating or between substrate layer and the 3rd hard conating.Described hard coating film may be used for the various touch panels such as capacitive way, resistive film mode, way of electromagnetic induction.Described hard coating film, except for except touch panel, also may be used for the various LCD MODULEs such as holographic display device.Described hard coating film, except being layered in except on touch panel, also may be used for the surface of strengthening the parts such as various optics, lens, dish, construction material and groceries.
Industrial applicibility
As mentioned above, hard coating film of the present invention, the transparent conductive laminate comprising this hard coating film and the touch panel comprising this transparent conductive laminate can improve the hardness of described hard coating film, and effectively can prevent curling, therefore can perform well in touch panel and other various LCD MODULEs.

Claims (12)

1. a hard coating film, is characterized in that,
Described hard coating film comprises:
Transparent substrate layer;
First hard conating, is formed at the side, a face of described substrate layer;
Second hard conating, is formed at the side, a face of described first hard conating; And
3rd hard conating, is formed at another side, face of described substrate layer,
The pencil hardness of described first hard conating is lower than the pencil hardness of described second hard conating,
The pencil hardness of described second hard conating is more than 3H,
The thickness of described first hard conating is more than 4 times less than 20 times of the thickness of described second hard conating,
The thickness of described second hard conating is more than 1 μm less than 10 μm,
The thickness of described 3rd hard conating is more than 50nm less than 10 μm,
The main component of described first hard conating is uv curing resin,
Described first hard conating contains UV resistant agent and polymerization initiator,
Described UV resistant agent is below more than 0.1 quality % 10 quality % relative to the content of the main component of described first hard conating, and described polymerization initiator is below more than 1 quality % 10 quality % relative to the content of the main component of described first hard conating.
2. hard coating film as claimed in claim 1, it is characterized in that, the pencil hardness of described first hard conating is more than F below H.
3. hard coating film as claimed in claim 1, it is characterized in that, the thickness of described first hard conating is more than 20 μm less than 100 μm.
4. hard coating film as claimed in claim 1, it is characterized in that, the pencil hardness of described substrate layer is more than 8B below F.
5. hard coating film as claimed in claim 1, it is characterized in that, the main component of described substrate layer is polycarbonate resin, cycloolefin resinoid or PETG resinoid.
6. hard coating film as claimed in claim 1, it is characterized in that, in the face of described substrate layer, length of delay Ro is below 100nm, and the thickness direction retardation value Rth of described substrate layer is below 200nm.
7. hard coating film as claimed in claim 1, it is characterized in that, described uv curing resin is cationically polymerizable resin.
8. hard coating film as claimed in claim 1, is characterized in that, in described 3rd hard conating, dispersion is containing high-refractive index particulate.
9. hard coating film as claimed in claim 8, it is characterized in that, the refractive index of described 3rd hard conating is less than more than 1.6 2.3.
10. a transparent conductive laminate, is characterized in that comprising:
Hard coating film described in claim 8 or 9; And
Transparency conducting layer, is laminated in another face of described 3rd hard conating.
11. transparent conductive laminates as claimed in claim 10, is characterized in that, the difference of the described refractive index of the 3rd hard conating and the refractive index of described transparency conducting layer is less than 0.6.
12. 1 kinds of touch panels, is characterized in that, described touch panel comprises transparent conductive laminate according to claim 10.
CN201210499264.7A 2011-12-01 2012-11-29 Hard coating film, transparent conductive laminate and touch panel Expired - Fee Related CN103129064B (en)

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