CN103129064A - Hard coat film, transparent conductive laminate and touch panel - Google Patents

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

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Publication number
CN103129064A
CN103129064A CN2012104992647A CN201210499264A CN103129064A CN 103129064 A CN103129064 A CN 103129064A CN 2012104992647 A CN2012104992647 A CN 2012104992647A CN 201210499264 A CN201210499264 A CN 201210499264A CN 103129064 A CN103129064 A CN 103129064A
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hard conating
hard
coating film
hard coating
conating
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CN103129064B (en
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赤松正
远藤大士
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EWA Co Ltd
Keiwa Inc
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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

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Position Input By Displaying (AREA)

Abstract

The purpose of the invention is to provide a hard coat film, a transparent conductive laminate and a touch panel having excellent hardness and capable of effectively preventing crimping. The transparent conductive laminate comprises the hard coat film and the touch panel comprises the transparent conductive laminate. The hard coat film provided by the invention comprises a transparent substrate layer, a first hard coating layer and a second hard coating layer and a third hard coating layer. Pencil hardness of the first hard coating layer is lower than that of the second hard coating layer. The pencil hardness of the second hard coating layer is more than 3H. Thickness of the first hard coating layer is 4 times-20 times of the thickness of the second hard coating layer. The thickness of the second hard coating layer is 1 mum-10 mum. The thickness of the third hard coating layer is 50 nm-10 mum.

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 the touch panel that comprises this transparent conductive laminate.
Background technology
LCD MODULE (LCD) has the features such as thin, lightweight, that power consumption is little, utilize described feature mostly LCD MODULE to be used as flat-panel monitor, and this purposes enlarges just year by year, can be used as the information display devices such as mobile phone, PDA(Personal Digital Assistant), PC, TV.In recent years, according to purposes, be various to the desired characteristic of LCD MODULE, as to the desired characteristic of LCD MODULE, can enumerate bright (high brightness), easily see (wide visual angle), energy-saving, slim lightweight and giant-screen etc.
For the ease for operation that improves the people who watches, rapid property etc., as described LCD MODULE, the LCD MODULE that touch panel is installed is arranged.In addition, the LCD MODULE that touch panel is installed has following structure usually: from face side to rear side, overlapping successively have touch panel, liquid crystal display cells, various optical sheet and a backlight.
As described touch panel, there is the touch panel of capacitive way, resistive film mode and way of electromagnetic induction etc.As capacitive way, have following mode: electrode is extended on cross one another direction, and when finger waited the contact touch panel, interelectrode electric capacity changed, and this capacitance variations is detected, and detects thus input position; And apply at the two ends of nesa coating the alternating current that phase place is identical, current potential is identical, thus produce weak current when finger contact or close formation electric capacity, detect this weak current, detect thus input position; Etc..
In described LCD MODULE, for resistance to impact and the usability that improves nesa coating and other optics can wait, mostly be provided with hard coating film on the surface of described optics.As described hard coating film, known have a hard coating film that has hard conating on the surface of substrate layer.As this hard coating film, patent documentation 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, be provided with the second hard conating (referring to No. 2000-71392, Japanese Patent Publication communique JP) on the surface of this first hard conating.The described hard coating film of this communique, be provided with the curing resin layer that formed by free-radical polymerised resin and cationically polymerizable resin blend thing on the surface of substrate layer as the first hard conating, be provided with essentially identical second hard conating of thickness of thickness and the first hard conating on the surface of this first hard conating, can keep marresistance thus, and can prevent crooked (カ ー Le) and can prevent crackle.
In addition, as the hard coating film with double-deck hard conating, patent documentation 2 discloses a kind of hard coating film, the pencil hardness that is compared to outer field the second hard conating as the pencil hardness of the first hard conating of internal layer is low, the thickness of Thickness Ratio second hard conating of the first hard conating thick (referring to No. 2007-219013, Japanese Patent Publication communique JP).The described hard coating film of this communique is by stacked the first hard conating that is formed by the low urethane acrylate that shrinks etc. of identical coating process and the second hard conating of being formed by the urethane acrylate of high rigidity etc., so the thickness of the second hard conating is thickness approximately over half of the first hard conating.
Yet, the hard coating film of described patent documentation 1, because the thickness of the first hard conating and the second hard conating is basic identical, therefore the first hard conating is thin, and the surface of hard coating film can't obtain enough hardness.In addition, if increase the thickness of hard conating in order to obtain enough hardness, the second hard conating can become blocked up, exists this hard coating film can produce curling problem.
In addition, the hard coating film of described patent documentation 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 thickness approximately over half of the first hard conating, therefore as its result, the surface of hard coating film can't obtain enough hardness, in addition, can not prevent reliably curling.
The prior art document
Patent documentation 1: No. 2000-71392, Japanese Patent Publication communique JP
Patent documentation 2: No. 2007-219013, Japanese Patent Publication communique JP
Summary of the invention
In view of described problem, the object of the present invention is to provide the hardness with excellence also can effectively prevent curling hard coating film, comprise the transparent conductive laminate of this hard coating film and the touch panel that comprises this transparent conductive laminate.
In order to solve described problem, the invention provides a kind of hard coating film, it comprises: transparent substrate layer; The first hard conating is formed at a face side of described substrate layer; The second hard conating is formed at a face side of described the first hard conating; And the 3rd hard conating, be formed at another face side of described substrate layer, the pencil hardness of described the first hard conating is lower than the pencil hardness of described the second hard conating, the pencil hardness of described the second hard conating is more than 3H, the thickness of described the first hard conating is more than 4 times below 20 times of thickness of described the second hard conating, the thickness of described the second hard conating is below the above 10 μ m of 1 μ m, and the thickness of described the 3rd hard conating is below the above 10 μ m of 50nm.
This hard coating film can improve the hardness of another face side by the 3rd hard conating that another face side at substrate layer forms.Particularly this hard coating film forms by the thickness that makes the 3rd hard conating and is thinned to more than 50nm below 10 μ m, can improve the hardness of another face side of substrate layer, and can prevent difference of hardness because of substrate layer and the 3rd hard conating cause produce curling.In addition, this hard coating film disposes 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 from causing that because of the nonhomogeneous hardness of substrate layer and the second hard conating generation is curling, and by the first hard conating and the second hard conating, can effectively improve the hardness of a face side of this hard coating film.Particularly the thickness by making the second hard conating is in described scope, and the thickness of the first hard conating is remained on more than 4 times in the scope below 20 times of thickness of the second hard conating, thus this hard coating film can prevent well pencil hardness because of the second hard conating higher 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, thus the hardness of two sides side can be improved and usability etc. can be improved, and can satisfy the requirement of slimming.
In described hard coating film, preferably, the pencil hardness of described the first hard conating is below the above H of F.Thus, can further effectively improve the hardness of a face side of hard coating film.
In described hard coating film, preferably, the thickness of described the first hard conating is below the above 100 μ m of 20 μ m.Thus, can further prevent well curling.
In described hard coating film, preferably, the pencil hardness of described substrate layer is below the above F of 8B.The pencil hardness of the substrate layer of this hard coating film is in the situation that described scope, and this hard coating film can prevent curling, and can improve well hardness.
In described hard coating film, preferably, the main component of described substrate layer is polycarbonate resin, cycloolefin resinoid or PETG resinoid.Thereby easily produce curling resin as the main component of substrate layer even hardness is lower in the situation that this hard coating film uses polycarbonate resin, cycloolefin resinoid or PETG resinoid etc., also can prevent curlingly, and can effectively improve hardness.By using polycarbonate resin, cycloolefin resinoid or PETG resinoid as the main component of substrate layer, this hard coating film can easily reduce length of delay (Ro) and thickness direction retardation value (Rth) in face.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 the cycloolefin resinoid as the main component of described substrate layer, this hard coating film can effectively suppress the variation of the phase difference that produces 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 the PETG resinoid as the main component of described substrate layer, this hard coating film can more effectively 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 with described hard coating film and the overlapping use of other optics, can prevent from damaging the optical function of other optics.
In described hard coating film, preferably, the main component of described the first hard conating is uv curing resin.Thus, can improve produceability.In addition, described hard coating film can prevent because substrate layer is heated thermal expansion or the thermal contraction that produces, thereby can improve dimensional stability.
In described hard coating film, in the situation that contain uv curing resin as the main component of described the first hard conating, preferably, described uv curing resin is the cationically polymerizable resin.Thus, can improve the cohesive of described the first hard conating and substrate layer, and can suppress bonding force and change in time.In addition, by using the cationically polymerizable resin as the main component of the first hard conating, described hard coating film can prevent curling, and can further improve dimensional stability.
In described hard coating film, preferably, described the first hard conating contain uv curing resin as main component in, described the first hard conating also contains UV resistant agent.Usually, be uv curing resin in the main component of the first hard conating, and in the situation that also contain UV resistant agent in this first hard conating, the curing rate of this first hard conating is slack-off, productivity ratio reduces.Yet, thicker due to the thickness setting of the first hard conating of described hard coating film, though therefore with the control of the concentration of UV resistant agent in the situation that low concentration also can contain the UV resistant agent of q.s in the first hard conating.Therefore, even in the situation that contain the anti-anti-outside line agent of q.s in the first hard conating, the curing rate that described hard coating film also can suppress the first hard conating reduces, thereby can prevent that productivity ratio from reducing.
In described hard coating film, preferably, disperse to contain high-refractive index particulate in described the 3rd hard conating.Thus, can improve the refractive index of the 3rd hard conating.
In described hard coating film, preferably, the refractive index of described the 3rd hard conating is more than 1.6 below 2.3.Thus, in the situation that the 3rd hard conating one 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 is approached, for example can make the refractive index of the 3rd hard conating near refractive index 2.1～2.2(λ of ITO=520nm).Its result, described hard coating film can reduce the observability of the electrode pattern that is 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 the 3rd hard conating.
Therefore this transparent conductive laminate can prevent well that described hard coating film from producing curling owing to comprising described hard coating film.In addition, this transparent conductive laminate also can improve usability so can improve the hardness of two sides side, and can satisfy the requirement of slimming owing to comprising described hard coating film.In addition, in this transparent conductive laminate, refractive index by making the 3rd hard conating and the refractive index of transparency conducting layer approach, thereby in the situation that described transparent conductive laminate for example is used for touch panel, can reduce the observability of the electrode pattern that is formed at transparency conducting layer.
In described transparent conductive laminate, preferably, the difference of the refractive index of described the 3rd hard conating and the refractive index of described transparency conducting layer is below 0.6.Thus, can further reduce the observability of the electrode pattern that is formed at transparency conducting layer.
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.
Therefore this touch panel can finely prevent that described hard coating film from producing curling owing to comprising described hard coating film.In addition, this touch panel also can improve usability etc. so can improve the hardness of two sides side, and can satisfy the requirement of slimming owing to comprising described hard coating film.In addition, the refractive index by making the 3rd hard conating and the refractive index of transparency conducting layer approach, and described touch panel can reduce the observability of the electrode pattern that is formed at transparency conducting layer thus.
In addition, in the present invention, the numerical value that the pencil cut value of putting down in writing in the test method that so-called " pencil hardness " refers to stipulate based on JIS K5600-5-4 obtains.In the present invention, all the pencil hardness than substrate layer is high to make the pencil hardness of the first hard conating, the pencil hardness of the second hard conating and the pencil hardness of the 3rd hard conating.So-called " thickness " refers to measure according to JIS K7130 the average thickness that obtains." face in length of delay (Ro) " is to pass through Ro=(Ny-Nx) * value that d obtains." thickness direction retardation value (Rth) " is to pass through Rth=((Nx+Ny)/value that 2-Nz) * d obtains.Wherein, Nx is the refractive index of the fast axle (axle parallel with the face direction) of film, Ny is the refractive index of the slow axis (parallel with the face direction and vertical with fast axle axle) of film, and Nz is the refractive index of the film on thickness direction (with the direction of face perpendicular direction), and d is the thickness of film.
So-called " UV resistant agent " refers to have the additive of the function that prevents that the light that causes because of ultraviolet ray is deteriorated, 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, comprise the transparent conductive laminate of this hard coating film and comprise that the touch panel of this transparent conductive laminate can improve the hardness of described hard coating film, and can effectively prevent curling.
Description of drawings
Fig. 1 means the schematic sectional view of the hard coating film of one embodiment of the present invention.
Fig. 2 means the schematic sectional view with the hard coating film of the hard coating film different modes of Fig. 1.
Fig. 3 means the schematic sectional view of the transparent conductive laminate of one embodiment of the present invention.
Fig. 4 means the schematic sectional view of the touch panel of one embodiment of the present invention.
Fig. 5 means 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
The specific embodiment
The first embodiment
Accompanying drawing below with reference to suitable is elaborated to embodiments of the present invention.
The hard coating film 1 of Fig. 1 comprises that substrate layer 2, face side hard conating 3 and rear side hard conating 4(are equivalent to the 3rd hard conating).In addition, in the situation that this hard coating film 1 is bonding with miscellaneous part, rear side hard conating 4 is disposed at the adhesive surface side, face side hard conating 3 is configured in an opposite side of adhesive surface.
Substrate layer 2
Substrate layer 2 can make light see through because of needs, thus be transparent, particularly water white.Although there is no particular limitation for the main component of formation substrate layer 2, is typically the group of selecting free polycarbonate resin, cycloolefin resinoid, acrylic resin, polypropylene-based resin and PETG resinoid to form.These synthetic resin have excellent optical transparence, and light is seen through well.Wherein, as the main component that consists of 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 contain other any composition, preferably substrate layer 2 contains the above main component that is made of described synthetic resin of 90 quality %, and more preferably substrate layer 2 contains the above main component that is made of described synthetic resin of 98 quality %.At this, as the example of any composition, can enumerate UV resistant agent, lubricant, processing aid, plasticizer, shock-resistant auxiliary agent, phase difference depressant, delustering agent, antiseptic, mould inhibitor etc.
As the polycarbonate resin that forms substrate layer 2, there is no particular limitation, can be only straight chain polycarbonate resin or branched polycarbonate resinoid any, can be also the polycarbonate resin that is consisted of by straight chain polycarbonate resin and branched polycarbonate resinoid.
The straight chain polycarbonate resin is the straight chain aromatic polycarbonate resins of making by known phosgenation or fusion method, is made by carbonic ester composition and bis-phenol (ジ Off ェ ノ ー Le) composition.Precursor as being used for importing the carbonic ester composition can exemplify phosgene, diphenyl carbonate etc.in addition, as bis-phenol, can exemplify 2, 2-two (4-hydroxy phenyl) propane, 2, 2-two (3, 5-dimethyl-4-hydroxy phenyl) propane, 1, 1-two (4-hydroxy phenyl) cyclohexane, 1, 1-two (3, 5-two mesyls-4-hydroxy phenyl) cyclohexane, 1, 1-two (4-hydroxy phenyl) decane, 1, 1-two (4-hydroxy phenyl) propane, 1, 1-two (4-hydroxy phenyl) cyclodecane, 1, 1-two (3, 5-dimethyl-4-hydroxy phenyl) cyclododecane, 4, 4 '-dihydroxy diphenyl ether, 4, 4 '-sulfo-biphenol, 4, 4 '-dihydroxy-3, 3-two ring diphenyl ether etc.These materials can use separately, also two or more combinations of substances can be used.Described straight chain polycarbonate resin can be by making such as the method for record in No. 3989672, US Patent No. etc., and its refractive index is preferably more than 1.57 below 1.59.
as the branched polycarbonate resinoid, be the polycarbonate resin that uses branching agent to make, as branching agent, can exemplify phloroglucin, trimellitic acid, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,2-three (4-hydroxy phenyl) ethane, 1,1,2-three (4-hydroxy phenyl) propane, 1,1,1-three (4-hydroxy phenyl) methane, 1,1,1-three (4-hydroxy phenyl) propane, 1,1,1-three (2-methyl-4-hydroxy phenyl) methane, 1,1,1-three (2-methyl-4-hydroxy phenyl) ethane, 1,1,1-three (3-methyl-4-hydroxy phenyl) methane, 1,1,1-three (3-methyl-4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) methane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 1,1,1-three (3-chloro-4-hydroxyl phenyl) methane, 1,1,1-three (3-chloro-4-hydroxyl phenyl) ethane, 1,1,1-three (3,5-, two chloro-4-hydroxy phenyls) methane, 1,1,1-three (3,5-, two chloro-4-hydroxy phenyls) ethane, 1,1,1-three (3-bromo-4-hydroxy phenyl) methane, 1,1,1-three (3-bromo-4-hydroxy phenyl) ethane, 1,1,1-three (3,5-, two bromo-4-hydroxy phenyls) methane, 1,1,1-three (3,5-, two bromo-4-hydroxy phenyls) ethane, 4,4 '-dihydroxy-2,5-dihydroxy diphenyl ether etc.
For example, enumerate as in No. 03-182524, Japanese Patent Publication communique Unexamined Patent, described branched polycarbonate resinoid can prepare by the following method: stir the reaction mixture that comprises the polycarbonate oligomer, aromatic series bisphenols and the end-capping reagent that are obtained by aromatic series bisphenols, described branching agent photoreactive gas, the limit reacts described material so that the mode of described reaction mixture formation turbulent flow stirs the limit to described reaction mixture, 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 above 80 following scopes of quality % of 5 quality %, preferably comprise the following scope of the above 60 quality % of 10 quality %.This be due to: when the branched polycarbonate resinoid during less than 5 quality %, have that tensile viscosity reduces, the problem of difficult forming in extrusion molding; When surpassing 80 quality %, there are the shear viscosity rising of resin, the problem of processing and forming reduction.
As the cycloolefin resinoid that forms substrate layer 2, so long as have the resin of the monomeric unit that is made of cyclic olefin (cycloolefin), just there is no particular limitation.As the cycloolefin resinoid that uses in substrate layer 2, can be any 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 as the copolymer of the alkene such as cyclic olefin and ethene.As cyclic olefin, there are the cyclic olefin of polycycle and the cyclic olefin of monocyclic.As the cyclic olefin of described polycycle, can enumerate ENB, methyl ENB, dimethyl ENB, ethyl ENB, ENB, butyl ENB, bicyclopentadiene, dihydro bicyclopentadiene, methyl bicyclic pentadiene, dimethyl bicyclopentadiene, tetracyclododecen, methyl tetracyclododecen, dimethyl tetracyclododecen, three cyclopentadiene, Fourth Ring pentadiene etc.In addition, as the cyclic olefin of monocyclic, can enumerate cyclobutane, cyclopentene, cyclo-octene, cyclo-octadiene, cyclo-octatriene, cyclodoecatriene etc.
The acrylic resin that forms substrate layer 2 is the resin that has from the skeleton of acrylic or methacrylic acid.example as acrylic resin, there is no particular limitation, can enumerate poly-(methyl) acrylate such as polymethyl methacrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) methyl acrylate-styrol copolymer, polymer (methyl methacrylate-cyclohexyl methacrylate copolymer for example with alicyclic alkyl, methyl methacrylate-(methyl) acrylic acid norborny ester copolymer) etc.In described acrylic resin, preferably gather poly-(methyl) acrylic acid C1-C6 Arrcostab, more preferably the methyl methacrylate resinoids such as (methyl) methyl acrylate.
The polypropylene-based resin that forms substrate layer 2 is the resin that has from the skeleton of propylene.As the example of polypropylene-based resin, there is no particular limitation, can enumerate homopolymers or the propylene of propylene and be selected from ethene and carbon number is more than one the copolymer of monomer in 4～12 alpha-olefin.
The PETG resinoid that forms substrate layer 2 is the polymer that is obtained by terephthalic acid (TPA) and glycol reaction.The PETG resinoid can also comprise other comonomer, and the repetitive of PETG is preferably more than 80mol%.PETG for example can prepare by following method: dimethyl terephthalate (DMT) and ethylene glycol are mixed in reactor, slowly raise internal temperature limit, limit makes reactant carry out ester exchange reaction, then product is moved in polymer reactor, carry out polymerisation under high-temperature vacuum, generate thus PETG.
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 the interior length of delay of the face of substrate layer 2 is 50nm more preferably, and further preferably 15nm, particularly preferably be 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 of the thickness direction retardation value of substrate layer 2 is 100nm more preferably, and further preferably 30nm, particularly preferably be 10nm.By reducing length of delay in 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 the optical function of this other optics is counteracted.
As the pencil hardness of substrate layer 2, although there is no particular limitation, for example in order further to improve the hardness after the affix hard conating, preferably the pencil hardness of substrate layer 2 is more high better, and the pencil hardness of substrate layer 2 can be for below the above F of 8B.Even the pencil hardness of substrate layer 2 is the degree of described scope, described hard coating film 1 also can prevent curling, and can be effectively the pencil hardness of a face side be brought up to degree below the above 6H of 2H.
As the thickness of substrate layer 2, there is no particular limitation, for example preferably below the above 200 μ m of 20 μ m.The higher limit of the thickness of substrate layer 2 is 150 μ m more preferably, particularly preferably are 100 μ m.On the other hand, the lower limit of the thickness of substrate layer 2 is 30 μ m more preferably, particularly preferably are 50 μ m.In the situation that the thickness of substrate layer 2 surpasses described higher limit, the speed of the production line in the time of can causing making and productivity ratio reduce, in addition, in the situation that described hard coating film 1 is used for liquid crystal indicator, there is the opposing problem that requires with the slimming that liquid crystal indicator is proposed.On the contrary, in the situation that the thickness of substrate layer 2 less than described lower limit, have intensity and less rigid, prevent the problems such as bending property reduction.
As substrate layer 2, usually using arithmetic mean surface roughness (Ra) is the substrate layer below 0.06 more than 0.02.In addition, in substrate layer 2, as required, can carry out unglazed processing.Implemented the arithmetic mean surface roughness (Ra) of substrate layer 2 of unglazed processing preferably more than 0.07 below 2, more preferably more than 0.1 below 1.By with the Roughness Surface on Control of substrate layer 2 in described scope, can prevent from producing damage in the processing after former film is made, can improve treatability.In addition, usually, when batching the former film that produces, need to carry out embossing processing (annular knurl processing is processed) to the two ends on the width of film and prevent into piece.When in the situation that carried out annular knurl processing on film and process, because the treatment sites at film two ends can not be used, so this part is must severing discarded.In addition, in film is batched operation, in order to prevent that the film injury is covered by diaphragm sometimes.Yet, be controlled in prescribed limit as above by the arithmetic mean surface roughness with substrate layer 2, need not to carry out annular knurl processing processing and just can prevent into piece, therefore manufacturing process is simple, two end portions on the width of film also can be used, and can batch along its length and can not produce the fault of film.In addition, substrate layer 2 sustains damage in the time of effectively suppressing to batch, and need not to cover as described above by having suitable surface roughness.
There is no particular limitation for the manufacture method of substrate layer 2, for example, the additives such as the tablet raw material of synthetic resin and plasticizer can be mixed according to present known mixed method, is pre-formed the thermoplastic resin composition, then makes substrate layer 2.Such as by with after the mixer premixeds such as the U.S. anti-mixer of Australia (omnimixer), extrude mixingly to obtaining mixture, can obtain described thermoplastic resin composition thus.In this case, there is no particular limitation to be used for extruding mixing mixing roll, can use the present known mixing rolls such as extruders such as going out machine such as single screw extrusion machine, twin-screw or pressurization kneader.
As the forming method of substrate layer 2, can exemplify the known methods such as solution casting method (solution casting method), extrusion by melting, rolling process, compression forming method.Wherein, preferably solution casting method (solution casting method), extrusion by melting.At this moment, can use and carry out in advance extruding mixing thermoplastic resin composition, also can be dissolved in respectively other additives such as synthetic resin and plasticizer in solvent, then they are formed uniform mixed solution, the film molding procedure to solution casting method (solution casting method) or extrusion by melting provides described mixed solution afterwards.In addition, for the length of delay of substrate layer 2 and the length of delay of hard coating film 1 are controlled to be necessarily, for example, can keep the chill roll of uniform temperature and endless belt to carry out cooling with the circular-arc molten resin that sandwiches to it by broad ways.
Solvent as using in solution casting method (solution casting method) can exemplify the chlorine kind solvents such as chloroform, carrene; Toluene, dimethylbenzene, benzene and their the aromatic series kind solvents such as 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 use a kind of, also may be used two or more.Device as being used for carrying out solution casting method (solution casting method) can exemplify drum-type casting machine, band casting machine, rotary coating machine etc.
As extrusion by melting, can enumerate T modulus method, blowing etc.Film forming temperature when melt extruding is preferably more than 150 ℃ below 350 ℃, more preferably more than 200 ℃ below 300 ℃.In the situation that form film by the T modulus method, can the T mould be installed at the leading section of known single screw extrusion machine or double screw extruder, batch and be extruded into membranaceous film, obtain thus the film of roller shape.At this moment, can be by suitably adjusting the temperature of takers-in, apply the processing that film is extended on direction extruding, can carry out the uniaxial tension operation thus.In addition, by with the direction of extruding perpendicular direction on increase the operation that film is extended, can increase successively the operations such as biaxial stretch-formed, simultaneously biaxial stretch-formed.
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 below the 21 above 105m of μ m.The higher limit of the thickness of face side hard conating 3 is 82 μ m more preferably, further preferably 63 μ m.On the other hand, the lower limit of the thickness of face side hard conating 3 is 32 μ m more preferably, further preferably 43 μ m.In the situation that the thickness of face side hard conating 3 surpasses described higher limit, basically not quite can promote to prevent curling effect, and existence and to the opposing problem that requires of the slimming of described hard coating film 1 proposition.On the contrary, in the situation that the thickness of face side hard conating 3 is less than described lower limit, existence can not prevent curling problem effectively.
The first hard conating 5
The first hard conating 5 is formed at a face of substrate layer 2.The first hard conating 5 can only be formed by resin, also can contain the additives such as UV resistant agent.As the main component that consists of the first hard conating 5, there is no particular limitation, can exemplify the active energy line curing resin or the resin that formed by the reactive silicon compound etc.As the active energy line curing resin, can enumerate uv curing resin, electronic beam curing resin, radiation-curable resin etc.In addition, as the reactive silicon compound, can enumerate tetraethoxysilane etc.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 owing to substrate layer 2 being applied thermal expansion or the thermal contraction that heat produces, thereby can improve dimensional stability.As described uv curing resin, can enumerate free-radical polymerised resin, cationically polymerizable resin etc.
As the polymerizable ultraviolet compound that forms described uv curing resin, can use by ultraviolet ray and can carry out monomer or the oligomer that polymerization, the reaction such as crosslinked are solidified.
As described monomer, can enumerate free radical polymerization monomer, cationically polymerizable monomer etc.In addition, as described oligomer, can enumerate radical polymerization oligomers, cationic polymerization oligomers etc.
As described free radical polymerization monomer, can exemplify 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 two cyclopentene esters; Two (methyl) acrylic acid DPG ester, two (methyl) acrylic acid 1, various (methyl) acrylate such as multifunctional (methyl) esters of acrylic acid such as 6-hexylene glycol ester, two (methyl) acrylic acid DOPCP, three (methyl) acrylic acid trihydroxymethylpropanyl ester, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester.
As described cationically polymerizable monomer, can exemplify 3,4-epoxide ring hexenyl methyl-3 ', the vinyl ethers such as the glycidol ethers such as alicyclic epoxy thing class, bisphenol A diglycidyl ether such as 4 '-epoxide ring hexenyl carboxylate, 4-hydroxybutyl vinyl ethers, 3-ethyl-oxetanes classes such as 3-hydroxymethyl oxetanes etc.
As described radical polymerization oligomers, can exemplify various (methyl) acrylate oligomers such as polyurethane (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, triazine (methyl) acrylate, silicon (methyl) acrylate; The polymercaptan quasi-oligomers such as trimethylolpropane tris mercaptoacetate, pentaerythrite four mercaptoacetates; Unsaturated polyester ester oligomer etc.
As described cationic polymerization oligomers, can the exemplified by novolak-type epoxy resin oligomer, aromatic ethenyl ether resin oligomer etc.
Wherein, as the polymerizable ultraviolet compound of the uv curing resin that is formed for the first hard conating 5, preferably cationically polymerizable monomer or cationic polymerization oligomers.
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 cationic polymerization oligomers as the polymerizable ultraviolet compound that forms described uv curing resin, can improve the cohesive of substrate layer 2 and the first hard conating 5, and can suppress bonding force and change in time.In addition, according to described structure, described hard coating film 1 can prevent the first hard conating 5 cure shrinkage, thereby can further improve dimensional stability.
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 that is obtained by these polymerizable compounds is usually higher.Therefore, by using alicyclic epoxy thing class or oxetanes class as the cationically polymerizable monomer that is used 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 ℃, more preferably more than 200 ℃, particularly preferably be more than 220 ℃.Glass transition temperature by making the cationically polymerizable resin is in described scope, and described hard coat film 1 can significantly improve heat resistance.
In addition, according to desired performance etc., the two or more mixing of described monomer and oligomer can be used.
In addition, as the polymerizable ultraviolet compound of the uv curing resin that is formed for the first hard conating 5, also preferably use the low free-radical polymerised compound of cure shrinkage.As this free-radical polymerised compound, can exemplify molecular weight and be 1000～3000 polymethyl acyloxy propyl group silsesquioxane (Port リ メ タ Network リ ロ キ シ プ ロ ピ Le シ Le セ ス キ オ キ サ Application).In addition, as the uv curing resin with described free-radical polymerised compound, for example also can use the free-radical polymerised resin of enumerating in No. 2008-120845, Japanese Patent Publication communique JP.
As contained polymerization initiator in the first hard conating 5, in the situation that the polymerizable ultraviolet compound is free-radical polymerised monomer or oligomer, can enumerate the compounds such as benzophenone, thioxanthene ketone, benzoin class, acetophenones.In addition, as contained polymerization initiator in the first hard conating 5, in the situation that the polymerizable ultraviolet compound is cationically polymerizable monomer or oligomer, can enumerate the compounds such as metallocene (メ タ ロ セ Application) class, aromatic matte class, aromatic series iodine class.
As the content of described polymerization initiator, there is no particular limitation, with respect to uv curing resin, preferably below the above 10 quality % of 1 quality %, more preferably below the above 6 quality % of 3 quality %.In the situation that the content of polymerization initiator surpasses described higher limit, the degree of polymerization of uv curing resin reduces, and existence can not obtain the problem of desirable hardness.On the contrary, in the situation that the problem that the content of polymerization initiator less than described lower limit, exists curing reaction fully not carry out.
In addition, in order to improve coating, the first hard conating 5 can also contain solvent.As this solvent, can exemplify the aliphatic hydrocarbons such as hexane, octane; 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 use separately, as required, also multiple mixing can be used.In addition, preferably, in the manufacturing process of the first hard conating 5, make described solvent evaporation, drying.That is, the boiling point of described solvent is preferably in the scope of 60～160 ℃.In addition, the saturated vapor of described solvent under 20 ℃ is pressed in the scope of 0.1～20kPa.For kind and the content of solvent, can suitably adjust according to the main component of the main component of substrate layer 2, the first hard conating 5 and thickness etc.
The first hard conating 5 can also contain UV resistant agent.As contained UV resistant agent in the first hard conating 5, can exemplify ultra-violet absorber, ultra-violet stabilizer etc.
As described ultra-violet absorber, can exemplify salicylic acid ultra-violet absorber, benzophenone ultra-violet absorber, Benzotriazole Ultraviolet Stabilizer, cyanoacrylate ultra-violet absorber, triazines ultra-violet absorber, benzoxazine ketone ultra-violet absorber etc., can use to be selected from one or more in described ultra-violet absorber.Wherein, from the viewpoint of dispersiveness, preferably triazines ultra-violet absorber, benzoxazine ketone ultra-violet absorber.In addition, as described ultra-violet absorber, preferably use the polymer that has the ultraviolet radiation absorption group in strand.By using this polymer that has the ultraviolet radiation absorption group in strand, can prevent the deterioration of the ultraviolet radiation absorption function that causes due to oozing out of ultra-violet absorber etc.As described ultraviolet radiation absorption group, can enumerate BTA base, benzophenone base, alpha-cyanoacrylate ester group, triazine radical, salicyl, benzylidene malonic acid ester group etc.Wherein, particularly preferably be BTA base, benzophenone base, triazine radical.
As described ultra-violet stabilizer, preferably use for example high to UV stable hindered amines ultra-violet stabilizer.By making the first hard conating 5 contain ultra-violet stabilizer, can make because of inertings such as free radical that ultraviolet ray produces, active oxygens, thereby improve for ultraviolet stability, weatherability etc.In addition, if the first hard conating 5 can significantly improve for ultraviolet smooth deterioration preventing performance and weatherability also with ultra-violet absorber and ultra-violet stabilizer.
As the content (mass ratio) of UV resistant agent with respect to the main component of the first hard conating 5, although there is no particular limitation, preferably below the above 10 quality % of 0.1 quality %.UV resistant agent is with respect to the upper limit of the content of the main component of the first hard conating 5 more preferably 8 quality %, further preferably 5 quality %.On the other hand, UV resistant agent is with respect to the lower limit of the content of the main component of the first hard conating 5 more preferably 1 quality %, further preferably 3 quality %.In the situation that the UV resistant agent of described hard coating film 1 surpasses the described upper limit with respect to the content of the main component of the first hard conating 5, the problem that exists the durability etc. of the first hard conating 5 to reduce.On the contrary, in the situation that the UV resistant agent of described hard coating film 1 with respect to the content of the main component of the first hard conating 5 less than described lower limit, exist the first hard conating 5 can not effectively realize the problem of anti-ultraviolet function.
Described hard coating film 1 preferably, the first hard conating 5 contains uv curing resin as main component, and contains UV resistant agent.Usually, are uv curing resins and in the situation that contain UV resistant agent in the first hard conating 5, the curing rate of the first hard conating 5 is slack-off, productivity ratio reduces in the main component of the first hard conating 5.Yet, because the thickness setting with the first hard conating 5 of described hard coating film 1 becomes thicker, even be therefore less concentration with the control of the concentration of UV resistant agent, also can make the UV resistant agent that contains q.s in the first hard conating 5.Therefore, even in the situation that contain the UV resistant agent of q.s in the first hard conating 5, the curing rate that described hard coating film 1 also can suppress the first hard conating 5 reduces, thereby can prevent that productivity ratio from reducing.In addition, in the situation that use polycarbonate resin as the main component of substrate layer 2, contain UV resistant agent by making the first hard conating 5, described hard coating film 1 can prevent the xanthochromia of substrate layer 2 etc. 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, need only the pencil hardness lower than the second hard conating 6, just there is no particular limitation, preferably below the above H of F.In the situation that the pencil hardness of the first hard conating 5 exceeds described higher limit, described hard coating film 1 produces curling possibility change greatly because of the difference of hardness of substrate layer 2 and the first hard conating 5.On the contrary, in the situation that the pencil hardness of the first hard conating 5 less than described lower limit, exists described hard coating film 1 can not obtain the problem of desirable hardness.
The thickness of the first hard conating 5 is more than 4 times below 20 times of thickness of the second hard conating 6.The upper limit of the thickness of the first hard conating 5 is 18 times of thickness of the second hard conating 6 more preferably, further preferably 16 times.In addition, the lower limit of the thickness of the first hard conating 5 is 6 times of thickness of the second hard conating 6 more preferably, further preferably 8 times.In the situation that the thickness of the first hard conating 5 surpasses the described upper limit, there is the problem that not quite can promote to prevent curling effect.On the contrary, in the situation that the thickness of the first hard conating 5 is less than described lower limit, existence can not prevent curling problem effectively.
In addition, as the thickness of the first hard conating 5, although there is no particular limitation, preferably below the above 100 μ m of 20 μ m.The higher limit of the thickness of the first hard conating 5 is 80 μ m more preferably, further preferably 60 μ m.On the other hand, the lower limit of the thickness of the first hard conating 5 is 30 μ m more preferably, further preferably 40 μ m.In the situation that the thickness of the first hard conating 5 surpasses described higher limit, have the problem that not quite can promote to prevent curling action, also with to the slimming of described hard coating film 1 proposition require opposing.On the contrary, in the situation that the thickness of the first hard conating 5 is less than described lower limit, existence can not prevent curling problem effectively.
As the tensile elasticity rate of the first hard conating 5, although there is no particular limitation, preferably below the above 4GPa of 1GPa.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.In the situation that the tensile elasticity rate of the first hard conating 5 surpasses described higher limit, existence can not prevent curling problem effectively.On the contrary, in the situation that the tensile elasticity rate of the first hard conating 5 less than described lower limit, exists described hard coating film 1 to be difficult to form the problem of desirable hardness.In addition, " tensile elasticity rate " in the present invention is to measure according to JIS K7113 the value that obtains.
In addition, the tensile elasticity rate of the first hard conating 5 be multiply by preferably 20kPamm of value that the cube of thickness obtains 3Above 500kPamm 3Below, 40kPamm more preferably 3Above 400kPamm 3Below, 60kPamm further preferably 3Above 300kPamm 3Below.Exceed described higher limit in the situation that the tensile elasticity rate of the first hard conating 5 be multiply by the value that the cube of thickness obtains, the rigidity of the first hard conating 5 becomes excessive, has the problem that is difficult to hard coating film 1 is remained the roller shape.On the contrary, in the situation that the tensile elasticity rate of the first hard conating 5 be multiply by value that the cube of thickness obtains less than described lower limit, exist the first hard conating 5 easily to be out of shape and be applied to the problem that the stress on substrate layer 2 can become excessive.
As the arithmetic average roughness (Ra) on the surface of a face side of the first hard conating 5, although there is no particular limitation, preferably below the above 8 μ m of 0.5 μ m.The higher limit of the arithmetic average roughness (Ra) on the surface of a face side of the first hard conating 5 is 7 μ m more preferably, further preferably 6 μ m.On the other hand, the lower limit of the arithmetic average roughness (Ra) on the surface of a face side of the first hard conating 5 is 1 μ m more preferably, particularly preferably is 2 μ m.In the situation that the arithmetic average roughness (Ra) on the surface of a face side of the first hard conating 5 surpasses described higher limit, have the problem of the thickness thickening that can make the second hard conating 6 that a face side at the first hard conating 5 forms.On the contrary, in the situation that the arithmetic average roughness (Ra) on the surface of a face side of the first hard conating 5 is less than described lower limit, the surface area of a face side of the first hard conating 5 is increased fully, therefore have the problem of the cohesive reduction of the first hard conating 5 and the second hard conating 6.On the other hand, at the arithmetic average roughness (Ra) of a face side surface of the first hard conating 5 in the situation that in described scope, can make the thickness of the second hard conating 6 remain suitable thickness, and can effectively 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 a face side of the first hard conating 5, although there is no particular limitation, preferably below the above 10 μ m of 0.5 μ m.The higher limit of 10 mean roughness (Rz) on the surface of a face side of the first hard conating 5 is 9 μ m more preferably, further preferably 8 μ m.On the other hand, the lower limit of 10 mean roughness (Rz) on the surface of a face side of the first hard conating 5 is 1 μ m more preferably, further preferably 2 μ m.In the situation that 10 mean roughness (Rz) on the surface of a face side of the first hard conating 5 surpass the described upper limit, exist the possibility of the thickness thickening that makes the second hard conating 6 can become large problem.On the contrary, in the situation that 10 mean roughness (Rz) on the surface of a face side of the first hard conating 5 are less than described lower limit, the surface area of a face side of the first hard conating 5 can not increase fully, therefore has the problem of the cohesive reduction of the first hard conating 5 and the second hard conating 6.In addition, " arithmetic average roughness (Ra) " and " 10 mean roughness (Rz) " is the value that obtains according to JISB0601-2001.
There is no particular limitation for the manufacture method of the first hard conating 5, can make resin drying by coating active energy line curing resin on a face of substrate layer 2, and the irradiation active energy ray is made the first hard conating 5.Coating process as the active energy line curing resin, so long as can evenly be coated with the method for active energy line curing resin on a face of substrate layer 2, just there is no particular limitation, can enumerate method of spin coating, spraying process, slope stream rubbing method, infusion process, rod and be coated with the whole bag of tricks such as method, rolling method, silk screen print method.In addition, in the manufacturing of the first hard conating 5, as required, as pre-treatment, can carry out the surface modification treatment such as plasma treatment under the inertness atmospheres such as argon gas or nitrogen.In addition, can also be on the surface of substrate layer 2 stacked priming coat, by stacked the first hard conating 5 of this priming coat.
The second hard conating 6
The second hard conating 6 is formed on a face of the first hard conating 5.As the material that forms the second hard conating 6, there is no particular limitation.The second hard conating 6 can only be formed by resin, also can contain therein the additives such as silicon dioxide microparticle.
Resin as forming the second hard conating 6 can exemplify thermosetting resin, active energy line curing resin etc.
For example 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 thus the second hard conating 6.
As the functional group of polymerizable monomer or the polyreactive oligomers of described active energy ray-curable, the functional group of ultraviolet ray, electron beam or radioactive ray polymerism preferably particularly preferably is polymerizable ultraviolet functional group.As polymerizable ultraviolet functional group, can enumerate the unsaturated polymerization of ethene such as (methyl) acryloyl group, vinyl, styryl, pi-allyl functional group etc.
As described coating composition, although there is no particular limitation, preferably with acrylic monomer or the urethane acrylate oligomer coating composition as main component.By forming the second hard conating 6 from the composition take described monomer or oligomer as main component, can improve the hardness of the second hard conating 6.Wherein, particularly preferably be from containing simultaneously composition formation second hard conating 6 of urethane acrylate and (methyl) acrylic compounds.
Total content as the urethane acrylate that forms the second hard conating 6 and (methyl) acrylic compounds, preferably below the above 99 quality % of 45 quality %, further preferably below the above 95 quality % of 50 quality %, particularly preferably be below the above 90 quality % of 60 quality %.Form the urethane acrylate of the second hard conating 6 and (methyl) if the total content of acrylic compounds surpasses the described upper limit, thereby have the photopolymerisable problem that can slack-offly cause productivity ratio to reduce of beginning.In addition, the urethane acrylate of formation the second hard conating 6 and (methyl) are if the problem that the total content of acrylic compounds less than described lower limit, exists flexibility, mar proof, marresistance etc. to reduce.On the other hand, form the urethane acrylate of the second hard conating 6 and (methyl) if the total content of acrylic compounds in described scope, can be boosted productivity, and can keep well suitable flexibility, mar proof and marresistance etc.
As described urethane acrylate, there is no particular limitation, can be any of monomer or oligomer.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 above 6 functional groups of 2 functional groups, further preferably below above 3 functional groups of 2 functional groups.Functional group's number by making urethane acrylate can keep the hardness of the second hard conating 6 and the balance of percentage elongation well in described scope.Urethane acrylate can use separately, also can be used in combination of two or more.
As the glass transition temperature of the resin that is formed by urethane acrylate, although there is no particular limitation, preferably more than 40 ℃ below 100 ℃, further preferably more than 40 ℃ below 80 ℃.Glass transition temperature by making the resin that is formed by urethane acrylate can improve hardness and the durability of the second hard conating 6 under normal temperature in described scope.
Content as the urethane acrylate that forms the second hard conating 6, although there is no particular limitation, but preferably below the above 90 quality % of 10 quality %, further preferably below the above 85 quality % of 15 quality %, particularly preferably be below the above 80 quality % of 20 quality %.Surpass the described upper limit, the problem that exists mar proof and hardness of film to reduce if form the content of the urethane acrylate of the second hard conating 6.In addition, if the content of urethane acrylate that forms the second hard conating 6 less than described lower limit, flexibility reduces, the possibility that cracks raises.On the other hand, if the content of urethane acrylate that forms the second hard conating 6 can keep suitable mar proof and hardness of film well in described scope, and can keep suitable flexibility and can suppress to crack.
As described (methyl) acrylic compounds, there is no particular limitation, can be any of monomer or oligomer.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 has (methyl) acrylic compounds more than 3 functional groups by use, can improve durability.In addition, described (methyl) acrylic compounds can be the molecular structure with polar group, can be also the molecular structure of low polarity.(methyl) acrylic compounds can be used separately, also can be used in combination of two or more.
As the polar group of (methyl) acrylic compounds, can enumerate hydroxyl, carboxyl, amino, amide groups etc.
as (methyl) acrylic compounds that contains hydroxyl, can exemplify (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, the 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic acid ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid esters that contain hydroxyl such as (methyl) acrylic acid 4-hydroxyl butyl ester etc.
As (methyl) acrylic compounds that contains carboxyl, except ethene unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, can also enumerate the 2-(methyl) acryloxy ethyl succinate, 2-(methyl) acryloxy ethylo benzene dicarboxylic acid esters, 2-(methyl) acryloxy ethyl six hydrogen terephthalate etc.
As containing amino (methyl) acrylic compounds, can exemplify (methyl) acrylic acid alkyl monosubstituted amino esters such as (methyl) acrylic acid monomethyl amino ethyl ester, (methyl) acrylic acid list ethylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid monomethyl, (methyl) acrylic acid list ethylamino propyl ester etc.
As (methyl) acrylic compounds that contains amide groups, can exemplify the acrylic amides such as (methyl) acrylamide, N-methyl (methyl) acrylamide, N-methylol (methyl) acrylamide etc.
In addition, (methyl) acrylic compounds as low polar molecular structure can exemplify (methyl) acrylate ring type ester or (methyl) alkyl acrylate.
As described (methyl) acrylate ring type ester, can exemplify (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.
As described (methyl) alkyl acrylate, can exemplify (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.
As (methyl) that form the second hard conating 6 although there is no particular limitation for the content of acrylic compounds, but preferably below the above 85 quality % of 5 quality %, further preferably below the above 80 quality % of 10 quality %, particularly preferably be below the above 75 quality % of 15 quality %.Form (methyl) of the second hard conating 6 if the content of acrylic compounds surpasses the described upper limit, the possibility that cracks when moulding increases.In addition, form (methyl) of the second hard conating 6 if the problem that the content of acrylic compounds less than described lower limit, exists mar proof and hardness of film to reduce.On the other hand, form (methyl) of the second hard conating 6 if the content of acrylic compounds in described scope, can keep suitable mar proof and hardness of film well, and can keep suitable flexibility and can suppress to crack.
as described polymerization initiator, can exemplify benzophenone, benzil, the tetramethyl michaelis ketone, CTX, 2, the 4-diethyl thioxanthone, benzoin ethyl ether, benzoin iso-propylether, the benzoin isobutyl ether, 2, the 2-diethoxy acetophenone, benzoin dimethylether, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the 1-hydroxycyclohexylphenylketone, the 2-methyl isophthalic acid-[the 4-(methyl mercapto) phenyl]-2-morpholinyl acetone-1, the 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, two (cyclopentadienyl group)-two (2, 6-two fluoro-3-(pyrroles-1-yl) titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide etc.In addition, described compound can use separately, also a plurality of mixing can be used.
The pencil hardness of the second hard conating 6 is more than 3H.The pencil hardness of the second hard conating 6 is more preferably more than 4H, further preferably more than 5H.In the situation that less than described lower limit, existing, the pencil hardness of the second hard conating 6 is difficult to make described hard coating film 1 to form the problem of desirable hardness.
The thickness of the second hard conating 6 is below the above 10 μ m of 1 μ m.The higher limit of the thickness of the second hard conating 6 is 8 μ m more preferably, further preferably 6 μ m.On the other hand, the lower limit of the thickness of the second hard conating 6 is 2 μ m more preferably, further preferably 3 μ m.In the situation that the thickness of the second hard conating 6 surpasses the described upper limit, can not effectively prevent curling, in addition also with the slimming that described hard coating film 1 is proposed require opposing.On the contrary, in the situation that less than described lower limit, existing, the thickness of the second hard conating 6 is difficult to make described hard coating film 1 to form the problem of desirable hardness.
As the tensile elasticity rate of the second hard conating 6, although there is no particular limitation, preferably below the above 6GPa of 1.5GPa.More preferably 5.5GPa, further preferably 5GPa of the higher limit of the tensile elasticity rate of described the second hard conating 6 in addition.On the other hand, the lower limit of the tensile elasticity rate of the second hard conating 6 is 2GPa more preferably, further preferably 2.5GPa.In the situation that the tensile elasticity rate of the second hard conating 6 surpasses the described upper limit, exist to be difficult to effectively prevent curling problem.On the contrary, in the situation that less than described lower limit, existing, the tensile elasticity rate of the second hard conating 6 is difficult to make described hard coating film 1 to form the problem of desirable 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 more than 1.5 below 4.The upper limit of the tensile elasticity rate of the second hard conating 6 and 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 lower limit of the tensile elasticity rate of the second hard conating 6 and the ratio of the tensile elasticity rate of the first hard conating 5 more preferably 1.7, further preferably 2.In the situation that the ratio of the tensile elasticity rate of the second hard conating 6 and the tensile elasticity rate of the first hard conating 5 surpasses the described upper limit, exist to be difficult to effectively prevent curling problem.On the contrary, in the situation that the ratio of the tensile elasticity rate of the second hard conating 6 and the tensile elasticity rate of the first hard conating 5 is less than described lower limit, existence can not improve the problem of the hardness of described hard conating 1 effectively.
There is no particular limitation for the manufacture method of the second hard conating 6, can make 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.The main component of formation rear side hard conating 4 is identical with the first hard conating 5.In addition, be contained in also identical with the first hard conating 5 of additive in rear side hard conating 4.
There is no particular limitation as the pencil hardness of rear side hard conating 4.In addition, adopt more than 50nm below 10 μ m as the thickness of rear side hard conating 4.The higher limit of the thickness of rear side hard conating 4 is 7 μ m more preferably, further preferably 5 μ m.On the other hand, the lower limit of the thickness of rear side hard conating 4 is 100nm more preferably, further preferably 200nm.The thickness of side hard conating 4 surpasses in the situation of described higher limit overleaf, has the problem that curling possibility can increase that occurs, and also opposing with the requirement of the slimming that described hard coating film 1 is proposed.On the contrary, in the situation of the thickness of side hard conating 4 less than described lower limit, existence can not realize the problem of desirable hardness overleaf.On the other hand, the thickness of side hard conating 4 be in the situation that in described scope, can improve well hardness overleaf, and can prevent curling and can promote the slimming of described hard coating film 1.
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 below 2%, more preferably below 1%, further preferably below 0.5%.In the situation that the mist degree of described hard coating film 1 surpasses described higher limit, exist the observability of image to descend and problem that the definition of shown image descends.
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%.In the situation that 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 see through, thus the problem that causes observability to descend.
The rear side hard conating 4 of another the face side of described hard coating film 1 by being formed at substrate layer 2 can improve the hardness of another face side.Particularly be thinned to described scope by the thickness that makes rear side hard conating 4, described hard coating film 1 can improve the hardness of another face side, and can prevent from causing that because of the difference of hardness of substrate layer 2 and rear side hard conating 4 generation is curling.In addition, between the substrate layer 2 and the second hard conating 6 of described hard coating film 1, be provided with pencil hardness first hard conating 5 lower than the pencil hardness of the second hard conating 6.Therefore, described hard coating film 1 can prevent from causing that because of the difference of hardness of substrate layer 2 and the second hard conating 6 generation is curling, and by the first hard conating 5 and the second hard conating 6, can effectively improve the hardness of a face side 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 is by the first hard conating 5, can effectively realize be used to preventing curling pooling feature, and can improve well the hardness of a face side of described hard coating film 1.Its result even 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 that forms, also can make described hard coating film 1 obtain desirable hardness.In addition, because the first hard conating 5, the second hard conating 6 and rear side hard conating 4 have described formation, so described hard coating film 1 can improve the hardness of two sides side, and can improve usability etc., and can satisfy the requirement of slimming.
Even in the situation that use the hardness such as polycarbonate resin, cycloolefin resinoid or PETG resinoid lower, easily produce curling resin as the main component of the substrate layer 2 of described hard coating film 1, described hard coating film 1 also can prevent curling, and can effectively improve hardness.By using polycarbonate resin, cycloolefin resinoid or PETG resinoid as the main component of substrate layer 2, described hard coating film 1 can easily reduce length of delay (Ro) and thickness direction retardation value (Rth) in face.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 the cycloolefin resinoid as the main component of substrate layer 2, described hard coating film 1 can suppress the variation of the phasic difference that the external force such as heating because of direct sunlight or display produce effectively, and can have excellent optical homogeneity, and can show meticulous image.By using the PETG resinoid as the main component of substrate layer 2, described hard coating film 1 can more effectively improve hardness.
The second embodiment
Hard coating film 11
The hard coating film 11 of Fig. 2 comprises that substrate layer 2, face side hard conating 3, rear side hard conating 12(are equivalent to the 3rd hard conating).Therefore substrate layer 2 in present embodiment and face side hard conating 3 have been given identical Reference numeral to them, and omitted their description due to identical with face side hard conating 3 with the substrate layer 2 of the hard coating film 1 of Fig. 1.
Rear side hard conating 12
Rear side hard conating 12 is formed at another face of substrate layer 2.Consist of rear side hard conating 12 main component (adhesive), be contained in the additive in rear side hard conating 12, pencil hardness and the thickness of rear side hard conating 12, identical with rear side hard conating 4 all.
Disperse to contain high-refractive index particulate in rear side hard conating 12.Described high-refractive index particulate as disperseing in rear side hard conating 12 to contain can exemplify ZnO, TiO 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 below the above 100nm of 1nm.The higher limit of the average grain diameter of described high-refractive index particulate is 80nm more preferably, further preferably 60nm.On the other hand, the lower limit of the average grain diameter of described high-refractive index particulate is 5nm more preferably, further preferably 10nm.In the situation that the average grain diameter of described high-refractive index particulate surpasses described higher limit, there is the problem of the transparency reduction of rear side hard conating 12.On the contrary, in the situation that the problem that the average grain diameter of described high-refractive index particulate less than described lower limit, exists the dispersiveness of high-refractive index particulate to reduce.
Manufacture method as rear side hard conating 12, for example described high-refractive index particulate can be dispersed in adhesive resin, after solvent dilution, utilize rolling method, method of spin coating, dip coating, spraying process, rod to be coated with the known coating processes such as method, knife coating, die coating method, ink jet type rubbing method, intaglio printing rubbing method, form described rear side hard conating 12.
As the content of described high-refractive index particulate with respect to adhesive, although there is no particular limitation, can be for example below the above 60 quality % of 10 quality %.
As the refractive index of rear side hard conating 12, although there is no particular limitation, preferably more than 1.6 below 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 the situation that in described scope overleaf, when the transparency conducting layer of the rear side hard conating 12 of described hard coating film 11 and touch panel etc. is stacked, it is large that the difference of the refractive index of rear side hard conating 12 and the refractive index of transparency conducting layer becomes, the problem that exists the observability of the electrode pattern that is formed at transparency conducting layer to increase.
Therefore described hard coating film 11 can improve the refractive index of rear side hard conating 12 owing to disperseing to contain high-refractive index particulate in rear side hard conating 12.In addition, the mist degree of described hard coating film 11 and luminous ray transmissivity and hard coating film 1 is identical.
The 3rd embodiment
Transparent conductive laminate 21
The transparent conductive laminate 21 of Fig. 3 comprises hard coating film 11 and transparency conducting layer 22.Therefore hard coating film 11 in present embodiment has been given identical Reference numeral to it, and has been omitted its description due to identical with the hard coating film 11 of Fig. 2.
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, so 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 the mineral-type metal, can exemplify gold, silver, copper, platinum, nickel, tin oxide, tin indium oxide (ITO) etc.As organic conductive macromolecule, can exemplify the organic conductive composition that has used polyaniline, polythiophene, polypyrrole, polyquinoxaline etc.Wherein, good ITO or the polythiophene class material of optical characteristics, outward appearance and electric conductivity preferably.
Method as the formation material of coating transparency conducting layer 22 on side hard conating 12 overleaf, there is no particular limitation, can adopt and be coated with the known coating processes such as method, knife coating, die coating method, ink jet type rubbing method, intaglio printing rubbing method such as rolling method, method of spin coating, dip coating, spraying process, rod.In addition, when the formation material of coating transparency conducting layer 22, in order to improve the being adjacent to property with rear side hard conating 12, also can carry out in advance the pre-treatments such as Corona discharge Treatment to rear side hard conating 12.
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 laser, electron beam accelerator, radioactive element isoreactivity energy line source etc.In addition, as the exposure of active energy ray, with the accumulative total quantometer under ultraviolet wavelength 365nm, preferably 50mJ/cm 2Above 5000mJ/cm 2Below.In the situation that exposure surpasses described higher limit, existence can cause the problem of active energy ray-curable coloring resin.On the contrary, in the situation that less than described lower limit, existing, exposure solidifies not enough problem.
In addition, also can form transparency conducting layer 22 by dry method such as sputtering methods.As the formation method of transparency conducting layer 22, from the being adjacent to property of rear side hard conating 12 and the viewpoint of slimming, preferably form the method for transparency conducting layer 22 by sputtering method.
The thickness of the transparency conducting layer 22 when forming by described sputtering method is although there is no particular limitation, preferably
Figure BDA00002496328100281
Above
Figure BDA00002496328100282
Below.The higher limit of transparency conducting layer 22 thickness when forming by described sputtering method more preferably
Figure BDA00002496328100283
Further preferably
Figure BDA00002496328100284
The lower limit of transparency conducting layer 22 thickness when forming by the described method of spattering on the other hand, more preferably
Figure BDA00002496328100285
Further preferably
Figure BDA00002496328100286
At the thickness of transparency conducting layer 22 in the situation that in described scope, can keep well electric conductivity and these both sides' of the transparency performance.In addition, even in the situation that the thickness of hard coating film 11 is thicker, the thickness by making transparency conducting layer 22 also can promote the slimming of described transparent conductive laminate 21 in described scope.
Therefore described transparent conductive laminate 21 can prevent well that hard coating film 11 from producing curling owing to comprising hard coating film 11.In addition, described transparent conductive laminate 21 is owing to comprising hard coating film 11, thus can effectively improve the hardness of the two sides side of hard coating film 11, and can improve usability, and can satisfy the requirement of slimming.In addition, the refractive index by making rear side hard conating 12 and the refractive index of transparency conducting layer 22 approach, in the situation that described transparent conductive laminate 21 for example is used for touch panel, can reduce the observability of the electrode pattern that is formed at transparency conducting layer 22.
Poor as the refractive index of the refractive index of rear side hard conating 12 and transparency conducting layer 22 is although there is no particular limitation, preferably below 0.6, more preferably below 0.5, further preferably below 0.3.The difference of the refractive index by making rear side hard conating 12 and the refractive index of transparency conducting layer 22 is in described scope, thereby described transparent conductive laminate 21 can further reduce the observability of the electrode pattern that is formed at transparency conducting layer 22.
The 4th embodiment touch panel 31
The touch panel 31 of Fig. 4 is touch panels of capacitive way.Touch panel 31 comprises transparent conductive laminate 21, glass substrate 32 and adhesive layer 33.Therefore transparent conductive laminate 21 in present embodiment has been given identical Reference numeral to it, and has been omitted its description due to identical with the transparent conductive laminate 21 of Fig. 3.
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 that has used the known resin of binding property such as acrylic resin, polyurethanes resin.So that being positioned at the mode of the face side (people's one side of watching) of transparency conducting layer 22, hard coating film 11 configures touch panel 31.
Therefore described touch panel 31 can prevent well that hard coating film 11 from producing curling owing to comprising hard coating film 11.Described touch panel 31 is owing to comprising hard coating film 11 in addition, and the hardness that therefore can improve the two sides side of hard coating film 11 also can improve usability, and can satisfy the requirement of slimming.In addition, the refractive index of the rear side hard conating 12 by making described touch panel 31 and the refractive index of transparency conducting layer 22 approach, and described touch panel 31 can reduce the observability of the electrode pattern that is formed at transparency conducting layer 22.
The 5th embodiment
Touch panel 41
The touch panel 41 of Fig. 5 is touch panels of resistive film mode.Touch panel 41 comprises transparent conductive laminate 21, a plurality of point-like sept 42, column spacer 43, transparency conducting layer 44, high refractive index layer 45 and glass substrate 46.So that being positioned at the mode of the face side of transparency conducting layer 22, hard coating film 11 configures touch panel 41.
A plurality of point-like septs 42 are formed at the surface of transparency conducting layer 44.Formation material as point-like sept 42 can exemplify the insulating resins such as epoxy resin or silicones.Column spacer 43 is arranged between transparency conducting layer 22 and transparency conducting layer 44.Formation material as column spacer 43 can exemplify the insulating resins such as epoxy resin, polyester, acrylic resin.Column spacer 43 be fixed on transparency conducting layer 22 rear side edge part and be fixed on the edge part of the face side of transparency conducting layer 44.Column spacer 43 is configured to make transparency conducting layer 22 and transparency conducting layer 44 to be 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, for example can be laminated in by adhesive layer (not shown) surface of glass substrate 46.
Described touch panel 41 is owing to comprising hard coating film 11, so it is curling to prevent well that hard coating film 11 from producing.Described touch panel 41 owing to comprising hard coating film 11, also can improve usability so can improve the hardness of the two sides side of hard coating film 11, and can satisfy the requirement of slimming in addition.In addition, the refractive index by making rear side hard conating 12 and the refractive index of transparency conducting layer 22 approach, and touch panel 41 can reduce the observability of the electrode pattern that is 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 the touch panel that comprises this transparent conductive laminate, except described mode, also can implement in the mode of various distortion, improvement.For example, described hard coating film also can be formed with adhesive layer in another face side.As this adhesive layer, can enumerate the adhesive layer that has used the known resin of binding property such as acrylic resin, polyurethanes resin.Can be by at another face side coat binding agent solution of substrate layer or high refractive index layer and make its drying form described adhesive layer.In addition, also can be by coat binding agent solution and make its drying on a face of release liners in advance, release liners and the 3rd hard conating that then will have adhesive are fitted, and form thus adhesive layer.
Replace disperseing to contain high-refractive index particulate in the 3rd hard conating of described hard coating film, described hard coating film can be also to disperse in the 3rd hard conating to contain high-refractive index particulate and contain the higher synthetic resin of refractive index ratio as main component.As such synthetic resin, can exemplify 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.Also can be on the second hard conating stacked other layer (such as UV absorbed layer, antistatic layer and anti-reflection layer etc.) of described hard coating film.Described hard coating film also can be between substrate layer and the first hard conating, have the intermediate layer between the first hard conating and the second hard conating or between substrate layer and the 3rd hard conating.Described hard coating film can be used for the various touch panels such as capacitive way, resistive film mode, way of electromagnetic induction.Described hard coating film also can be used for the various LCD MODULEs such as holographic display device except being used for touch panel.Described hard coating film on being layered in touch panel, also can be used for the surface strengthen the parts such as various opticses, lens, dish, construction material and groceries.
Industrial applicibility
As mentioned above, hard coating film of the present invention, comprise the transparent conductive laminate of this hard coating film and comprise that the touch panel of this transparent conductive laminate can improve the hardness of described hard coating film, therefore and can effectively prevent curlingly, can perform well in touch panel and other various LCD MODULEs.

Claims (14)

1. a hard coating film, is characterized in that,
Described hard coating film comprises:
Transparent substrate layer;
The first hard conating is formed at a face side of described substrate layer;
The second hard conating is formed at a face side of described the first hard conating; And
The 3rd hard conating is formed at another face side of described substrate layer,
The pencil hardness of described the first hard conating is lower than the pencil hardness of described the second hard conating,
The pencil hardness of described the second hard conating is more than 3H,
The thickness of described the first hard conating is more than 4 times below 20 times of thickness of described the second hard conating,
The thickness of described the second hard conating is below the above 10 μ m of 1 μ m,
The thickness of described the 3rd hard conating is below the above 10 μ m of 50nm.
2. hard coating film as claimed in claim 1, is characterized in that, the pencil hardness of described the first hard conating is below the above H of F.
3. hard coating film as claimed in claim 1, is characterized in that, the thickness of described the first hard conating is below the above 100 μ m of 20 μ m.
4. hard coating film as claimed in claim 1, is characterized in that, the pencil hardness of described substrate layer is below the above F of 8B.
5. hard coating film as claimed in claim 1, 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, 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, is characterized in that, the main component of described the first hard conating is uv curing resin.
8. hard coating film as claimed in claim 7, is characterized in that, described uv curing resin is the cationically polymerizable resin.
9. hard coating film as claimed in claim 7, is characterized in that, described the first hard conating contains UV resistant agent.
10. hard coating film as claimed in claim 1, is characterized in that, disperses to contain high-refractive index particulate in described the 3rd hard conating.
11. hard coating film as claimed in claim 10 is characterized in that, the refractive index of described the 3rd hard conating is more than 1.6 below 2.3.
12. a transparent conductive laminate is characterized in that comprising:
The described hard coating film of claim 10 or 11; And
Transparency conducting layer is laminated in another face of described the 3rd hard conating.
13. transparent conductive laminate as claimed in claim 12 is characterized in that, the difference of the refractive index of described the 3rd hard conating and the refractive index of described transparency conducting layer is below 0.6.
14. a touch panel is characterized in that, described touch panel comprises the described transparent conductive laminate of claim 12.
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CN110600164B (en) * 2018-06-12 2022-12-02 日东电工株式会社 Hard coating film and transparent conductive film

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CN103129064B (en) 2015-12-23
JP2013117584A (en) 2013-06-13
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KR20130061641A (en) 2013-06-11
KR101426725B1 (en) 2014-08-06
TW201323220A (en) 2013-06-16

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