CN104067352B - Transparent conductive film, touch panel, and display device - Google Patents

Transparent conductive film, touch panel, and display device Download PDF

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Publication number
CN104067352B
CN104067352B CN201380006513.7A CN201380006513A CN104067352B CN 104067352 B CN104067352 B CN 104067352B CN 201380006513 A CN201380006513 A CN 201380006513A CN 104067352 B CN104067352 B CN 104067352B
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adhesive linkage
easy adhesive
transparent
electrically conductive
refractive index
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CN104067352A (en
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桐本高代志
中道夏树
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Toray Advanced Film Co Ltd
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Toray Advanced Film Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G02B1/116—Multilayers including electrically conducting layers
    • 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
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • 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
    • G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Human Computer Interaction (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Position Input By Displaying (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

Provided is a low cost, transparent conductive film having good antireflection properties. The transparent conductive film: has a transparent conductive membrane on one surface of a base material film having a refractive index of 1.6-1.7; and has only one low-refractive index layer having a refractive index of no more than 1.42 and a thickness of 80-120 nm, on the other surface of the base material film, having a highly adhesive layer therebetween. The highly adhesive layer fulfills condition 1, condition 2, or condition 1 and condition 2. Condition 1: The absolute value for the difference between the refractive index of the base material film and the refractive index of the highly adhesive layer is no more than 0.08. Condition 2: The thickness of the highly adhesive layer is at least 5 nm and less than 50 nm.

Description

Transparent and electrically conductive film, touch panel and display unit
Technical field
The present invention relates to the transparent and electrically conductive film that a kind of photopermeability is good, specifically relate to a kind of use have in the touch panel of transparent and electrically conductive film and display unit the transparent and electrically conductive film that the permeability from the light of display floater can be suppressed to reduce.
Background technology
For the transparent and electrically conductive film that touch panel etc. uses, there will be a known in order to give the marresistance that touches input face or for extraneous light antireflection and in the functional layer (patent documentation 1,2) such as opposing face (for base material film, being the face contrary with the face being provided with nesa coating) laminated hard conating, anti-reflection layer, antiglare layer of transparent and electrically conductive film.
In addition, the existence possessing the internal voids layer (air layer) of the display unit of touch panel can increase the boundary reflection of transparent and electrically conductive film and air layer, and the unfavorable condition reduced and so on from the permeability of the light of display floater can occur thus.In order to solve this problem, there will be a known the inside (patent documentation 3,4) that will the transparent and electrically conductive film of anti-reflection layer had to be used for touch panel or display unit at the mask contrary with nesa coating.
Patent documentation 1: Japanese Unexamined Patent Publication 11-34206 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-15941 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2000-321558 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-90458 publication
Summary of the invention
Describe in above-mentioned patent documentation and multilayer can be adopted to form or individual layer formation as anti-reflection layer.But, when multilayer is formed, although easily obtain high antireflection, there is the problem of production cost (productivity ratio is low) or easily produce the problem of interference fringe and so on.When anti-reflection layer be individual layer form, although be low cost, there is the problem of sufficient antireflection and so on of cannot obtaining, marresistance reduce, the problem of sliding or resistance to blocking reduction and so on.In addition, in above-mentioned patent documentation, concrete record be there is no to the anti-reflection layer of individual layer.
Thus, the object of the invention is to, provide a kind of low cost and the good transparent and electrically conductive film of antireflection.Other object of the present invention is, the touch panel providing a kind of use to have transparent and electrically conductive film of the present invention and the display unit possessing described touch panel.
Above-mentioned purpose of the present invention realizes by invention below.
1) a kind of transparent and electrically conductive film, it is characterized in that, be that the one side of the base material film of 1.6 ~ 1.7 has nesa coating in refractive index, only have one deck refractive index at the another side of described base material film across easy adhesive linkage and be less than 1.42 and thickness is the low-index layer of 80 ~ 120nm, described easy adhesive linkage meets following condition 1.
Condition 1: the absolute value of the refractive index of base material film and the specific refractivity of easy adhesive linkage is less than 0.08.
2) a kind of transparent and electrically conductive film, it is characterized in that, be that the one side of the base material film of 1.6 ~ 1.7 has nesa coating in refractive index, only have one deck refractive index at the another side of described base material film across easy adhesive linkage and be less than 1.42 and thickness is the low-index layer of 80 ~ 120nm, described easy adhesive linkage meets following condition 2.
Condition 2: easily the thickness of adhesive linkage is more than 5nm and is less than 50nm.
3) a kind of transparent and electrically conductive film, it is characterized in that, be that the one side of the base material film of 1.6 ~ 1.7 has nesa coating in refractive index, only have one deck refractive index at the another side of described base material film across easy adhesive linkage and be less than 1.42 and thickness is the low-index layer of 80 ~ 120nm, described easy adhesive linkage meets following condition 1 and condition 2.
Condition 1: the absolute value of the refractive index of base material film and the specific refractivity of easy adhesive linkage is less than 0.08.
Condition 2: easily the thickness of adhesive linkage is more than 5nm and is less than 50nm.
4) as above-mentioned 1) or 3) as described in transparent and electrically conductive film, wherein, the absolute value of the refractive index of described base material film and the specific refractivity of easy adhesive linkage is less than 0.05.
5) as above-mentioned 1) or 4) as described in transparent and electrically conductive film, wherein, the thickness of described easy adhesive linkage is more than 5nm and is less than 200nm.
6) as above-mentioned 1) ~ 5) according to any one of transparent and electrically conductive film, wherein, described base material film is polyester film.
7) as above-mentioned 6) as described in transparent and electrically conductive film, wherein, described polyester film is PETG film.
8) as above-mentioned 1) ~ 7) according to any one of transparent and electrically conductive film, wherein, described easy adhesive linkage is at least containing resin and crosslinking agent.
9) as above-mentioned 8) as described in transparent and electrically conductive film, wherein, described resin is mylar.
10) as above-mentioned 1) ~ 9) according to any one of transparent and electrically conductive film, wherein, described low-index layer is by the coat activated energy line curing resin composition of wet coating method and the layer making it solidify.
11) as above-mentioned 1) ~ 10) according to any one of transparent and electrically conductive film, wherein, described easy adhesive linkage comprises particle, and the relation of the average grain diameter (r) of described particle and the thickness (d) of easy adhesive linkage meets following formula 1.
0.5≤(r/d)≤20 formula 1
12) as above-mentioned 11) as described in transparent and electrically conductive film, wherein, relative to the solid state component total amount 100 quality % of described easy adhesive linkage, the described particle containing 0.05 ~ 20 quality %.
13) as above-mentioned 1) ~ 12) according to any one of transparent and electrically conductive film, wherein, described low-index layer contains the polysiloxane compound with ethylenic unsaturated group (ethylenic unsaturatedgroup).
14) touch panel, it possesses above-mentioned 1) ~ 13) according to any one of transparent and electrically conductive film.
15) a kind of display unit, it is configured with use on a display panel to have above-mentioned 1) ~ 13) according to any one of the display unit of touch panel of transparent and electrically conductive film, described display unit configures across the mode that air layer is relative with display floater with the described low-index layer side of described transparent and electrically conductive film.
16) a kind of display unit, it is configured with use on a display panel to have above-mentioned 1) ~ 13) according to any one of the display unit of electromagnetic wave shielding component of transparent and electrically conductive film, described display unit configures across the mode that air layer is relative with display floater with the described low-index layer side of described transparent and electrically conductive film.
According to the present invention, low cost can be provided and the good transparent and electrically conductive film of antireflection.In addition, by having the touch panel of transparent and electrically conductive film of the present invention and/or electromagnetic wave shielding component to be configured at display unit use, can provide from the good display unit of the permeability of the light of display floater.
In addition, according to optimal way of the present invention, sliding can be provided to obtain the transparent and electrically conductive film improved.
In addition, according to optimal way of the present invention, the transparent and electrically conductive film that oligomer can be suppressed to separate out from base material film can be provided.
Accompanying drawing explanation
Fig. 1 possesses the generalized section using and have an example of the display unit of the resistive touch panel of transparent and electrically conductive film of the present invention.
Fig. 2 possesses the generalized section using and have an example of the display unit of the capacitive touch panels of transparent and electrically conductive film of the present invention.
Fig. 3 possesses the generalized section using and have an example of the display unit of the capacitive touch panels of transparent and electrically conductive film of the present invention.
Fig. 4 possesses the generalized section using and have an example of the display unit of the electromagnetic wave shielding component of transparent and electrically conductive film of the present invention.
Embodiment
For transparent and electrically conductive film of the present invention, in the one side of base material film, there is nesa coating, across easy adhesive linkage, only there is one deck low-index layer at the another side of described base material film.Below, each inscape of transparent and electrically conductive film of the present invention is described in detail.
[base material film]
Base material film of the present invention be refractive index 1.6 ~ 1.7 the film of scope.From the viewpoint of the reflectivity of interface reducing low-index layer and air layer, the refractive index of preferred substrates film is large.Specifically, the refractive index of base material film be preferably more than 1.61, be more preferably more than 1.62, more preferably more than 1.63, be particularly preferably more than 1.64.
Base material film of the present invention can be selected from plastic film.In plastic film, from the viewpoint of hot strength, thermal endurance, solvent resistance, preferably use polyester film, particularly preferably use PETG film (PET film).
The appropriate thickness of base material film is the scope of 20 ~ 300 μm, is preferably the scope of 30 ~ 200 μm, is more preferably the scope of 50 ~ 150 μm.
[easy adhesive linkage]
Easy adhesive linkage of the present invention is the adaptation for strengthening base material film and low-index layer, and the combination of utilization and base material film and low-index layer described later simultaneously maintains the layer of excellent antireflection (antiradar reflectivity).In order to maintain excellent antireflection, easy adhesive linkage must meet following condition 1, condition 2 or (condition 1 and condition 2).Particularly preferably easily adhesive linkage satisfies condition 1.
Condition 1: the absolute value of the refractive index of base material film and the specific refractivity of easy adhesive linkage is less than 0.08.
Condition 2: easily the thickness of adhesive linkage is more than 5nm and is less than 50nm.
The easy adhesive linkage of 1 [satisfy condition]
The easy adhesive linkage of condition 1 to be the absolute value meeting the refractive index of base material film and the specific refractivity of easy adhesive linkage be less than 0.08 easy adhesive linkage.The absolute value of above-mentioned refringence is preferably less than 0.06, is more preferably less than 0.05, is particularly preferably less than 0.03, most preferably is less than 0.01.If the absolute value of the specific refractivity of the refractive index of base material film and easy adhesive linkage is greater than 0.08, then cannot obtain good antireflection.
Strengthen the meaning of the adaptation of base material film and low-index layer based on easy adhesive linkage, preferably easily the hardness of adhesive linkage itself is not too high.Transparent and electrically conductive film of the present invention only has the low-index layer of very thin films on easy adhesive linkage, therefore, if the thickness of the easy adhesive linkage making hardness not too high increases, then and the unfavorable condition of hardness reduction that low-index layer occurs sometimes and so on.Thus, preferably easily the thickness of adhesive linkage is smaller.
Consider from above-mentioned viewpoint, specifically, the thickness of easy adhesive linkage is preferably less than 200nm, is more preferably less than 150nm, is preferably less than 130nm further, is particularly preferably less than 100nm.From the viewpoint of the adaptation guaranteeing base material film and low-index layer, the thickness of lower limit is preferably more than 5nm, is more preferably more than 10nm, more preferably more than 20nm.
The easy adhesive linkage of condition 1 is the easy adhesive linkage that refractive index ratio is larger, and above-mentioned easy adhesive linkage can obtain by making it contain the high-index materials such as the larger resin of refractive index ratio or metal oxide microparticle.
Knownly easy adhesive linkage can be set on PETG film.The refractive index of PETG film is generally about 1.63 ~ 1.67, easy adhesive linkage laminated at present usually with resins such as mylar, acrylic resin, carbamate resins for main component, refractive index is usually smaller, is about 1.50 ~ 1.54, does not satisfy condition 1.
A kind of mode of the easy adhesive linkage of condition 1 is: use by importing aromatic ring, sulphur atom, bromine atoms etc. and the resin of high index of refraction in the resins such as mylar, acrylic resin, carbamate resins.Relative to the solid state component total amount 100 quality % of easy adhesive linkage, the content of the resin of above-mentioned high index of refraction is preferably more than 50 quality %, is more preferably more than 60 quality %, is particularly preferably more than 70 quality %.The content of the upper limit is about 98 quality %.
Resin as above-mentioned high index of refraction, has the mylar of aromatic ring in preferred molecule, preferably have the mylar of condensation aromatic ring further in molecule.As above-mentioned condensation aromatic ring, such as, naphthalene nucleus, fluorenes ring etc. can be enumerated.
Mylar can be obtained by carboxylic acid composition and diol component polycondensation usually.The mylar in above-mentioned molecule with naphthalene nucleus can be synthesized as carboxylic acid composition by the dicarboxylic acids using Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, NDA etc. to have naphthalene nucleus.The refractive index in molecule with the mylar of naphthalene nucleus can control by regulating the ratio with the dicarboxylic acids of naphthalene nucleus in whole carboxylic acid composition.
The mylar in above-mentioned molecule with fluorenes ring can synthesize as carboxylic acid composition and/or diol component by using the compound with fluorenes ring.By regulating the above-mentioned content with the compound of fluorenes ring, the refractive index of this mylar can be controlled.For the mylar in molecule with fluorenes ring, such as, be documented in No. WO2009/145075, International Publication, can synthesize with reference to it.
Above-mentioned mylar is preferably water-soluble or water dispersible.The mylar of water-soluble or water dispersible can be synthesized by the polybasic carboxylic acid that makes to comprise in the carboxylic acid composition that uses in mylar synthesis more than 3 yuan or the dicarboxylic acids with sulfo group.
The alternate manner of the easy adhesive linkage of condition 1 is: make it contain metal oxide microparticle.The easy adhesive linkage of which is the layer being dispersed with metal oxide microparticle in resin.As resin, can use such as: the mylar etc. in acrylic resin (preferred acrylic resin polyalcohol etc. have the acrylic resin of OH base), mylar (preferred polyester resin polyalcohol etc. have the mylar of OH base), epoxy resin, carbamate resins, styrene-maleic acid grafted polyester resin, acrylic acid-grafted mylar, organic siliconresin or above-mentioned molecule with condensation aromatic ring.
As metal oxide microparticle, titanium oxide, zirconia, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonates, tin oxide can be used to mix indium oxide (ITO), antimony doped tin oxide (ATO), mix phosphorus oxidation tin, Al-Doped ZnO, gallium-doped zinc oxide etc.In these metal oxide microparticles, from the viewpoint of the transparency, light resistance, high index of refraction, preferential oxidation titanium and zirconia, particularly preferably zirconia.
For the resin in easy adhesive linkage and metal oxide microparticle containing ratio, by quality ratio, be suitably the scope of 100:10 ~ 100:400, be preferably the scope of 100:20 ~ 100:300, be particularly preferably the scope of 100:30 ~ 100:200.
The easy adhesive linkage of 2 [satisfy condition]
For the easy adhesive linkage of condition 2, its thickness is more than 5nm and is less than the scope of 50nm.If easily the thickness of adhesive linkage is more than 50nm, then cannot obtain antiradar reflectivity, on the contrary, if easily the thickness of adhesive linkage is less than 5nm, then the adaptation of low-index layer reduces.Even if the thickness of the easy adhesive linkage of condition 2 is also preferably less in the scope of above-mentioned thickness, specifically, is preferably less than 40nm, is more preferably less than 30nm.The thickness of the lower limit of easy adhesive linkage is preferably more than 10nm.
The refractive index of the easy adhesive linkage of condition 2 is not particularly limited, be preferably more than 1.45 and be less than 1.60 scope, be more preferably the scope of 1.47 ~ 1.59, be particularly preferably the scope of 1.48 ~ 1.58.
The easy adhesive linkage of condition 2 preferably comprises the layer of the resins such as mylar, acrylic resin, carbamate resins.
In addition, the easy adhesive linkage of condition 2 can use the easy adhesive linkage of the composition same with above-mentioned condition 1.
[the easy adhesive linkage of satisfy condition 1 and condition 2]
As easy adhesive linkage of the present invention, the easy adhesive linkage of simultaneously satisfy condition 1 and condition 2 can be used.
[the easy adhesive linkage of condition 1 and the general content of the easy adhesive linkage of condition 2]
Below, the content that the easy adhesive linkage of condition 1 and condition 2 is general is described.
For easy adhesive linkage of the present invention, as mentioned above, preferably at least comprise resin.As above-mentioned resin, preferably at least comprise mylar.Wrap the details of resiniferous easy adhesive linkage as described later, in the manufacturing process of polyester film, the online laminated easy adhesive linkage of energy is useful in productivity ratio.Relative to the solid state component total amount 100 quality % of easy adhesive linkage, the content of the resin in easy adhesive linkage is preferably more than 20 quality %, is more preferably more than 30 quality %, is particularly preferably more than 50 quality %.The upper limit is about 98 quality %.
Easy adhesive linkage is preferably containing crosslinking agent.As above-mentioned crosslinking agent, melamine series crosslinking agent, oxazoline system crosslinking agent, carbodiimide system crosslinking agent, isocyanate-based crosslinking agent, aziridine system crosslinking agent, epoxy crosslinking agent can be used, through methylolation or alkanolized urea system crosslinking agent, acrylamide crosslinking agent, polyamide series resin, amide epoxy compound, various silane coupler, various titanate esters systems coupling agent etc.In these crosslinking agents, preferably use at least one in the group be made up of melamine series crosslinking agent, oxazoline system crosslinking agent, carbodiimide system crosslinking agent, isocyanate-based crosslinking agent and aziridine system crosslinking agent.
Relative to the solid state component total amount 100 quality % of easy adhesive linkage, the scope that the content of the crosslinking agent in easy adhesive linkage is preferably the scope of 1 ~ 40 quality %, is more preferably the scope of 3 ~ 35 quality %, is particularly preferably 5 ~ 30 quality %.
Easy adhesive linkage is preferably at least containing resin and crosslinking agent.Thus, the adaptation of base material film and low-index layer improves further.
In addition, so easy adhesive linkage (at least containing the easy adhesive linkage of resin and crosslinking agent) is laminated on base material film, and on this easy adhesive linkage laminated low-index layer described later (by the coat activated energy line curing resin composition of wet coating method and the low-index layer making it solidify), oligomer can be suppressed thus to separate out from base material film.
When using PETG film as base material film, if carry out heat treated in the film making process etc. of nesa coating described later, then sometimes separate out on the surface of PETG film as the oligomer (cyclic trimer) of non-crosslinked composition.By laminated easy adhesive linkage (the easy adhesive linkage at least containing resin and crosslinking agent) and low-index layer (by the coat activated energy line curing resin composition of wet coating method and the low-index layer making it solidify), this oligomer can be suppressed to separate out.
And then separate out from the viewpoint of suppression oligomer, the thickness of easy adhesive linkage is preferably more than 50nm, is more preferably more than 60nm, is particularly preferably more than 70nm.
Easy adhesive linkage is preferably further containing particle.When and the low-index layer of thin (80 ~ 120nm) level and smooth containing only one deck laminated on the easy adhesive linkage of particle, the convex structure produced by the particle of easy adhesive linkage also can be reflected in low-index layer, even if its result is after laminated low-index layer, also can improves the sliding on low-index layer surface and maintain good resistance to blocking.
Consider from above-mentioned viewpoint, the average grain diameter (r) of the particle preferably easily contained by adhesive linkage is larger relative to the ratio of the thickness (d) of easy adhesive linkage.Specifically, preferably meet following formula 1, preferably meet following formula 2 further, particularly preferably meet following formula 3.
0.5≤(r/d)≤20 formula 1
1.0≤(r/d)≤10 formula 2
1.3≤(r/d)≤6 formula 3.
The average grain diameter of the particle contained by easy adhesive linkage is preferably selected in the scope of above-mentioned formula 1 ~ 3, specifically, and the scope that the average grain diameter of particle is preferably the scope of 10 ~ 600nm, is more preferably the scope of 20 ~ 500nm, is particularly preferably 30 ~ 300nm.It should be noted that, the average grain diameter of the particle contained by easy adhesive linkage is the particle diameter on average obtained by quantity.
Relative to the solid state component total amount 100 quality % of easy adhesive linkage, the scope that the content of the particle in easy adhesive linkage is preferably the scope of 0.05 ~ 20 quality %, is more preferably the scope of 0.1 ~ 15 quality %, is particularly preferably 0.2 ~ 10 quality %.
As the particle contained by easy adhesive linkage, be not particularly limited, can enumerate: the inorganic particulates such as silicon dioxide granule, titanium oxide, aluminium oxide, zirconia, calcium carbonate, carbon black, zeolite particles; The organic filler such as acrylic particles, organosilicon particle, polyimide particle, Teflon (registered trade mark) particle, cross-linked polyester particle, crosslinked polystyrene particle, cross-linking polymer particle, core-shell type particle.Wherein, preferred silicon dioxide granule, particularly preferably cataloid.
Easy adhesive linkage of the present invention is laminated on base material film preferably by wet coating method, further the so-called online rubbing method of preferred laminated easy adhesive linkage in the manufacturing process of base material film.As wet coating method, can enumerate such as: reverse roll rubbing method, spraying rubbing method, bar type rubbing method, gravure coating process, scale metered application method (rod coat method) ,, die coating methods etc.
When base material film is coated with easy adhesive linkage of the present invention, as the preliminary treatment for improving coating, adaptation, preferably Corona discharge Treatment, flame treatment, plasma treatment etc. are implemented in advance to base material film surface.
For above-mentioned online rubbing method, the following describes the mode using PETG (below referred to as PET) film as base material film, but the present invention is not limited thereto.
Be after the PET particle vacuumize of 0.5 ~ 0.8dl/g using the inherent viscosity of the raw material as PET film, be supplied to extruder and melting at 260 ~ 300 DEG C, extruded with sheet by T font nozzle, use the casting method applying electrostatic, the minute surface casting cylinder being wound on surface temperature 10 ~ 60 DEG C makes its cooling curing, thus makes and not stretch PET film.Make this PET film that do not stretch longitudinally (refer to the direct of travel of film, also referred to as " length direction ") between the roller being heated to 70 ~ 100 DEG C to stretch 2.5 ~ 5 times.In atmosphere Corona discharge Treatment is implemented at least one side of the uniaxial tension PET film obtained by this stretching, make the wetting tension on this surface be more than 47mN/m, at the coating fluid of this treated side coating easy adhesive linkage of the present invention.
Then, be coated with the uniaxial tension PET film of coating fluid with fixture holding and import arid region, at the temperature of Tg being less than uniaxial tension PET film after drying, rise to the temperature of more than Tg, dry at temperature again near Tg, and then the continuous heating region at 70 ~ 150 DEG C transversely (refers to the direction of the direct of travel perpendicular to film, also referred to as " Width ") stretch 2.5 ~ 5 times, next implement heat treatment 5 ~ 40 seconds at the heating region of 180 ~ 240 DEG C, the laminated polyester film having easy adhesive linkage in the PET film that finishes at crystalline orientation can be obtained.It should be noted that, in above-mentioned heat treatment, also can implement the relaxation processes of 3 ~ 12% as required.Biaxial stretch-formed can be longitudinally, laterally successively stretch or simultaneously biaxial stretch-formed in any one, in addition also can after longitudinal direction, cross directional stretch, longitudinally, laterally in any one direction redraw.
From the viewpoint of the adaptation strengthening base material film and low-index layer, easy adhesive linkage of the present invention is not preferably the resin bed be cured by ultraviolet or electron beam isoreactivity energy line.Such as, when replacing easy adhesive linkage and be directly laminated on base material film by the high refractive index layer of active energy ray-curable, the adaptation of base material film and high refractive index layer cannot be obtained fully.
(low-index layer)
Low-index layer of the present invention is that refractive index is less than 1.42 and thickness is the layer of 80 ~ 120nm.The refractive index of low-index layer is preferably less than 1.41, is more preferably less than 1.40, is particularly preferably less than 1.39.Being not particularly limited the refractive index of lower limit, is about 1.30.
If the refractive index of low-index layer is greater than 1.42, then cannot obtain good antireflection.In addition, when the thickness of low-index layer departs from the scope of 80 ~ 120nm, also good antireflection cannot be obtained.
The thickness of low-index layer is preferably the scope of 85 ~ 115nm, is particularly preferably the scope of 90 ~ 110nm.
As a kind of mode of low-index layer, metal fluoride film can be enumerated.This metal fluoride film is by the laminated film of the gas phase masking methods such as vacuum vapour deposition, reactive vapour deposition method, Assisted by Ion Beam vapour deposition method, sputtering method, ion plating method, plasma CVD method.
As above-mentioned metal fluoride, can enumerate such as: magnesium fluoride (MgF 2), aluminum fluoride (AlF 3), calcirm-fluoride (CaF 2), barium fluoride (BaF 2), strontium fluoride (SrF 2), ice crystal (Na 3alF 6), chiolite (Na 5al 3f 14), sodium fluoride (NaF) etc.Wherein, preferably magnesium fluoride can be used.
The optimal way of low-index layer is by the coat activated energy ray-curable composition of wet coating method and the layer making it solidify.
As wet coating method, the such as coating process such as reverse roll rubbing method, spraying rubbing method, bar type rubbing method, gravure coating process, scale metered application method, die coating methods, method of spin coating, extrusion coated method can be used.
As active energy ray-curable composition, such as, the active energy ray-curable resin comprising and be cured by ultraviolet, electron beam isoreactivity energy line can be enumerated and as the low-refraction inorganic particulate of low-index material and/or the composition of fluorochemical.
Active energy ray-curable resin is the resin be cured by ultraviolet or electron beam isoreactivity energy line, preferably uses monomer or the oligomer at least in molecule with 1 ethylenic unsaturated group.Here, as ethylenic unsaturated group, acryloyl group, methacryl, acryloxy, methacryloxy, vinyl, pi-allyl etc. can be enumerated.It should be noted that, in the following description, " (methyl) acrylate " this expression comprises " acrylate " and " methacrylate " two kinds of compounds.
As the example of above-mentioned monomer, can enumerate: the monofunctional acrylates such as (methyl) methyl acrylate, (methyl) lauryl acrylate, ethoxydiglycol (methyl) acrylate, methoxy triglycol (methyl) acrylate, (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxyl-3-benzene oxygen ester, neopentyl glycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol three (methyl) acrylate, tripentaerythritol six (methyl) triacrylate, trimethylolpropane (methyl) acrylic acid benzoic ether, the polyfunctional acrylic esters such as trimethylolpropane benzoic ether, the urethane acrylates etc. such as glycerine two (methyl) acrylate hexamethylene diisocyanate, pentaerythrite three (methyl) acrylate hexamethylene diisocyanate.
As the example of above-mentioned oligomer, polyester (methyl) acrylate, polyurethane (methyl) acrylate, epoxy (methyl) acrylate, polyethers (methyl) acrylate, alkyd (methyl) acrylate, melamine (methyl) acrylate, organosilicon (methyl) acrylate etc. can be enumerated.
Above-mentioned monomer or oligomer can be used alone or multiple mixing uses, and preferably use 3 officials can above polyfunctional monomer or multifunctional oligomer.
In active energy ray-curable composition, relative to the solid state component total amount 100 quality % of composition, the content of active energy ray-curable resin can be suitably the scope of 5 ~ 90 quality %, is preferably the scope of 5 ~ 80 quality %, is more preferably the scope of 10 ~ 70 quality %.
As low-refraction inorganic particulate, the inorganic particulates such as preferred silicon dioxide or magnesium fluoride.Preferably these inorganic particulates are the particle of hollow form or Porous further.The refractive index of above-mentioned inorganic particulate is more preferably the scope of 1.2 ~ 1.35.
In active energy ray-curable composition, relative to the solid state component total amount 100 quality % of composition, the scope that the content of low-refraction inorganic particulate is preferably the scope of 20 ~ 70 quality %, is more preferably the scope of 25 ~ 70 quality %, is particularly preferably 30 ~ 60 quality %.
As fluorochemical, fluorochemical monomer, fluorine-containing oligomer, fluorine-containing polymer compound can be enumerated.Here, fluorochemical monomer, fluorine-containing oligomer are monomer or the oligomer in molecule with ethylenic unsaturated group and fluorine atom.
As fluorochemical monomer, fluorine-containing oligomer, such as, can enumerate: 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3,3-five fluoropropyl (methyl) acrylate, 2-(perfluoro butyl) ethyl (methyl) acrylate, 2-(perfluoro hexyl) ethyl (methyl) acrylate, 2-(perfluoro capryl) ethyl (methyl) acrylate, 2-(perfluoro decyl) ethyl (methyl) acrylate, fluorine-containing (methyl) esters of acrylic acids such as β-(perfluoro capryl) ethyl (methyl) acrylate, two (α-perfluoroalkyl acrylate)-2,2,2-trifluoroethyl ethylene glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,3-five fluoropropyl ethylene glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,4,4,4-seven fluorine butyl glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,4,4,5,5,5-nine fluorine amyl group ethylene glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,4,4,5,5,6,6,6-11 fluorine hexyl ethylene glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,4,4,5,5,6,6,7,7,7-ten trifluoro heptyl ethylene glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-15 fluorine octyl group ethylene glycol, two (α-perfluoroalkyl acrylate)-3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl group ethylene glycol, two (α-perfluoroalkyl acrylate)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-17 two (α-perfluoroalkyl acrylate) fluoroalkyl ester class such as fluorine nonyl ethylene glycol.
As fluorine-containing polymer compound, such as, can enumerate fluorochemical monomer and the fluorinated copolymer of monomer as Component units being used for giving crosslinkable groups.As the concrete example of fluorine-containing monomer unit, be such as fluoroolefins class (such as PVF, vinylidene fluoride, tetrafluoroethene, hexafluoroethylene, hexafluoropropylene, perfluor-2,2-dimethyl-1,3-dioxole etc.), (methyl) acrylic acid partially or completely fluorinated alkyl ester derivant class (such as Biscoat6FM (manufacture of Osaka organic chemistry) or M-2020 (DAIKIN manufacture) etc.), wholly or in part fluorinated vinyl ethers etc.As the monomer for giving crosslinkable groups, except (methyl) acrylate monomer in advance in molecule as glycidyl methacrylate with cross-linking functional group, also can enumerate (methyl) acrylate monomer (such as (methyl) acrylic acid, (methyl) acrylic acid methylol ester, (methyl) acrylic acid hydroxy alkyl ester, allyl acrylate etc.) with carboxyl or hydroxyl, amino, sulfonic group etc.
In active energy ray-curable composition, relative to the solid state component total amount 100 quality % of composition, the content of fluorochemical is preferably more than 30 quality %, is more preferably more than 50 quality %, is particularly preferably more than 60 quality %.The upper limit is preferably below 100 quality %, is more preferably below 99 quality %, is particularly preferably below 98 quality %.
For active energy ray-curable composition, whole or a part of as active energy ray-curable resin, can use aforesaid fluorochemical monomer and/or fluorine-containing oligomer.
Active energy ray-curable composition preferably comprises Photoepolymerizationinitiater initiater.As the concrete example of above-mentioned Photoepolymerizationinitiater initiater, can use such as: acetophenone, 2, 2-diethoxy acetophenone, to dimethyl acetophenone, to dimethylamino propiophenone, benzophenone, 2-chlorobenzophenone, 4, 4 '-dichloro benzophenone, 4, 4 '-bis-diethylamino benzophenone, Michler's keton, benzil, benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, methyl benzoylformate (Methyl Benzoylformate), p-isopropyl-Alpha-hydroxy isobutyl group benzophenone, Alpha-hydroxy isobutyl group benzophenone, 2, 2-dimethoxy-2-phenyl acetophenone, the carbonyls such as 1-hydroxycyclohexyl phenyl ketone, tetra methylthiuram list sulfide, tetramethyl thiuram disulfide, thioxanthones, CTX, the sulphur compounds etc. such as 2-methyl thioxanthones.These Photoepolymerizationinitiater initiaters may be used alone, two or more kinds can also be used in combination.
Relative to the solid state component total amount 100 quality % of composition, the content of above-mentioned Photoepolymerizationinitiater initiater can be suitably the scope of 0.1 ~ 10 quality %, the scope being preferably 0.5 ~ 8 quality %.
In order to improve sliding or the marresistance on low-index layer surface, active energy ray-curable composition is preferably containing the polysiloxane compound with ethylenic unsaturated group.
The polysiloxane compound with ethylenic unsaturated group is the compound that any one position in the end of polysiloxane backbone in the molecule or side chain has more than 1 ethylenic unsaturated group.As ethylenic unsaturated group, can enumerate: vinyl, pi-allyl, acryloyl group, methacryl, acryloxy, methacryloxy etc.The quantity with the ethylenic unsaturated group in the polysiloxane compound of ethylenic unsaturated group is preferably the scope of 1 ~ 6.In addition, as the polysiloxane compound with ethylenic unsaturated group, preferably there is the polydimethylsiloxane compound of ethylenic unsaturated group.
As the polysiloxane compound with ethylenic unsaturated group, can use: X-24-8201, X-22-174DX, X-22-2426, X-22-2404, X-22-164A, X-22-164C, Dow Corning TorayCo. that Silaplane FM-0711, Silaplane FM-0721 that the compound of the Production Example 1-1 ~ 1-3 of Japanese Unexamined Patent Publication 2009-84327 publication or ChissoCorporation manufacture, SilaplaneFM-0725, Shin-Etsu Chemial Co., Ltd manufacture, the commercially available products such as BY16-152D, BY16-152, BY16-152C that Ltd. manufactures.
Relative to the solid state component total amount 100 quality % of active energy ray-curable composition, the content with the polysiloxane compound of ethylenic unsaturated group be preferably more than 0.5 quality % and be less than the scope of 10 quality %, be more preferably more than 1 quality % and be less than 8 quality % scope, more preferably more than 1.3 quality % and be less than 6 quality % scope, be particularly preferably more than 1.5 quality % and be less than the scope of 5 quality %.
As mentioned above, easy adhesive linkage contains particle, and low-index layer contains the polysiloxane compound with ethylenic unsaturated group, and the sliding on low-index layer surface improves further thus, and the resistance to blocking in production process etc. improves.
In addition, when low-index layer be by the coat activated energy line curing resin composition of wet coating method and the layer making it solidify, oligomer can be suppressed to separate out from base material film.
As mentioned above, when using PETG film as base material film, if carry out heat treated in the film making process etc. of nesa coating described later, then sometimes separate out on the surface of PETG film as the oligomer (cyclic trimer) of non-crosslinked composition.By laminated above-mentioned easy adhesive linkage (the easy adhesive linkage at least containing resin and crosslinking agent) and low-index layer (by the coat activated energy line curing resin composition of wet coating method and the low-index layer making it solidify), this oligomer can be suppressed to separate out.
And then separate out from the viewpoint of suppression oligomer, the thickness of low-index layer is preferably more than 80nm, is more preferably more than 90nm.
In transparent and electrically conductive film of the present invention, the visual reflection rate of low-index layer side is preferably less than 1.0%, is more preferably less than 0.9%, is particularly preferably less than 0.8%, most preferably is less than 0.7%.If the visual reflection rate of the low-index layer side of transparent and electrically conductive film is greater than 1.0%, then from the light of display floater transmitance reduce and the display quality of display unit is reduced.
[nesa coating]
As the material of nesa coating, the known material that the electrode of touch panel uses can be used.Such as can enumerate: the metal nanometer line such as metal oxide, nano silver wire, the carbon nano-tube etc. such as tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (tin indium oxide), ATO (antimony tin).Wherein, preferably ITO can be used.
Such as, for the thickness of nesa coating, from guaranteeing that sheet resistance value is 10 3the viewpoint of the good conductivity of Ω/below is considered, is preferably more than 10nm, is more preferably more than 15nm, is particularly preferably more than 20nm.On the other hand, if the thickness of nesa coating is excessive, the inhibition of perspective phenomenon is then made to diminish sometimes, and there is the unfavorable condition of transparency reduction and so on, therefore, the upper limit of the thickness of nesa coating be preferably below 100nm, be more preferably below 60nm, more preferably below 50nm, be particularly preferably below 40nm.
As the formation method of nesa coating, be not particularly limited, current known method can be used.Specifically, the dry processes such as such as vacuum vapour deposition, sputtering method, ion plating method or wet coating method (being specifically preceding method) can be used.
The nesa coating of masking described above can carry out patterning.The purposes that patterning can be applied according to transparent and electrically conductive film forms various pattern.It should be noted that, by the patterning of nesa coating, drafting department and non-drafting department can be formed, as the shape of drafting department, such as, striated, clathrate or their combination pattern etc. can be enumerated.
The patterning of nesa coating utilizes etching to carry out usually.Such as, on nesa coating, formed the resist film of pattern-like by photo-engraving process, laser explosure method or print process, then carry out etch processes, make electrically conducting transparent film patterning thus.
As etching solution, current known etching solution can be used.Such as, the organic acids such as inorganic acid, acetic acid such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid and their mixture and their aqueous solution can be used.
[other functional layer]
Between base material film and nesa coating, other functional layer is preferably set.As other functional layer, easy adhesive linkage, hard conating, high refractive index layer, low-index layer etc. can be enumerated, these functional layers can be arranged separately or combine setting.
As the easy adhesive linkage be arranged between base material film and nesa coating, can use easy adhesive linkage similar to the above, particularly preferably refractive index is the easy adhesive linkage of the scope of 1.55 ~ 1.60.In addition, thickness is preferably the scope of 10 ~ 200nm.
Hard conating is coated with the active energy line curing composition the layer making it solidify that comprise above-mentioned active energy ray-curable resin preferably by wet coating method.The refractive index of hard conating is suitably the scope of 1.48 ~ 1.55, is preferably the scope of 1.50 ~ 1.53.
High refractive index layer comprises preferably by wet coating method coating the metal oxide microparticle (titanium oxide that refractive index is more than 1.65, zirconia, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonates, tin oxide mixes indium oxide (ITO), antimony doped tin oxide (ATO), mix phosphorus oxidation tin, Al-Doped ZnO, gallium-doped zinc oxide, fluorine doped tin oxide etc.) and the active energy line curing composition of above-mentioned active energy ray-curable resin the layer making it solidify.
The refractive index (n1) of high refractive index layer is preferably the scope of 1.61 ~ 1.80, is more preferably the scope of 1.63 ~ 1.75.The thickness (d1) of high refractive index layer is preferably the scope of 30 ~ 100nm, is more preferably the scope of 40 ~ 95nm.
Low-index layer can use the layer same with above-mentioned low-index layer.In addition, also preferably SiO is used 2film (being formed by gas phase masking method) is as low-index layer.The refractive index (n2) of low-index layer is preferably the scope of 1.30 ~ 1.50, is more preferably the scope of 1.33 ~ 1.48.The thickness (d2) of low-index layer be more preferably 5 ~ 70nm scope, be more preferably the scope of 7 ~ 50nm, be particularly preferably the scope of 10 ~ 45nm.
Particularly preferably in arranging high refractive index layer and low-index layer between base material film and nesa coating.By arranging high refractive index layer and low-index layer, the reflected colour caused by the tone of nesa coating of transparent and electrically conductive film or the unfavorable condition of transmitted colour can be revised.Now, the total of the optical thickness of high refractive index layer and the optical thickness of low-index layer is preferably λ/4.
Here, optical thickness is that refractive index and thickness are long-pending, and λ is the wave-length coverage i.e. 380 ~ 780nm of visible region.The unit of thickness is nm.
That is, the total of the optical thickness of high refractive index layer and the optical thickness of low-index layer preferably meets relational expression 4 below.
(380nm/4)≦(n1×d1)+(n2×d2)≦(780nm/4)
95nm≤(n1 × d1)+(n2 × d2)≤195nm (formula 4)
As mentioned above, between base material film and nesa coating, be arranged through the coat activated energy line curing composition of wet coating method and the layer making it solidify, be namely selected from hard conating, high refractive index layer and low-index layer at least 1 layer, can prevent oligomer from separating out from base material film thus.
[touch panel and display unit]
Transparent and electrically conductive film of the present invention is preferred for the touch panel of resistance membrane type or condenser type etc.Be particularly preferred for capacitive touch panels.
Resistive touch panel is generally with the nesa coating of 2 transparent and electrically conductive films each other across the formation that the mode that spacer is relative is configured.
Fig. 1 is the generalized section of an example of the display unit possessing resistive touch panel (use has transparent and electrically conductive film of the present invention).Fig. 1 uses transparent and electrically conductive film 11 of the present invention as the scheme of lower electrode.Form touch panel 21 by the transparent and electrically conductive film 12 forming upper electrode with the transparent and electrically conductive film 11 forming lower electrode, touch panel 21 is configured on display floater 31 across air layer 9.
For touch panel 21, transparent and electrically conductive film 11 (have nesa coating 2 in the one side of base material film 1 and only have one deck low-index layer 4 at the another side of base material film 1 across easy adhesive linkage 3) of the present invention is configured across the mode that spacer 8 is relative to make nesa coating 2 and 6 with transparent and electrically conductive film 12 (have nesa coating 6 in the one side of base material film 5 and have functional layer 7 at the another side of base material film 5).Air layer 9 is there is in low-index layer 4 side of transparent and electrically conductive film 11 of the present invention.
Due to the existence of this air layer 9, become greatly with the reflectivity of the interface of transparent and electrically conductive film 11, the transmitance from the light of display floater is reduced, display quality (brightness or visuognosis degree) also can be made to reduce as display unit.But the transparent and electrically conductive film of the application of the invention, can reduce boundary reflection, can guarantee good display quality.
As display floater 31, display panels or organic EL display panel can be enumerated.As the functional layer of transparent and electrically conductive film 12, hard conating, antiglare layer, anti-reflection layer, stain-proofing layer etc. can be used.
Fig. 2 and Fig. 3 is the generalized section of an example of the display unit possessing capacitive touch panels (use has transparent and electrically conductive film of the present invention).
Fig. 2 is the generalized section of the display unit possessing the capacitive touch panels that X electrode and Y electrode configure across air layer.X electrode is made up of transparent and electrically conductive film 13 of the present invention, and Y electrode is made up of transparent and electrically conductive film 14 of the present invention, and 2 transparent and electrically conductive films 13 and 14 configure across air layer 9 and form touch panel 22.And touch panel 22 is configured on display floater 31 across air layer 9.
For forming the transparent and electrically conductive film of the present invention 13 and 14 of X electrode and Y electrode, in the one side of base material film 1, there is nesa coating 2 and across easy adhesive linkage 3, only there is one deck low-index layer 4 at the another side of base material film 1.X electrode and Y electrode are by being formed nesa coating 2 patterning respectively.
The respective low-index layer 4 of transparent and electrically conductive film 13 and 14 of the present invention contacts with air layer 9.
In fig. 2, transparent and electrically conductive film 13 and 14 can pass through adhesive phase (not shown) and bonds.Now, because the low-index layer of transparent and electrically conductive film 13 does not contact with air layer, therefore, transparent and electrically conductive film 13 does not necessarily use transparent and electrically conductive film of the present invention.
Fig. 3 is the generalized section of the display unit possessing following capacitive touch panels, and this capacitive touch panels employs the transparent and electrically conductive film being formed with X electrode and Y electrode on 1 base material film.The formation of the nesa coating 2 of transparent and electrically conductive film 15 of the present invention is, the nesa coating forming the nesa coating of the patterning of X electrode and the patterning of formation Y electrode carries out laminated across dielectric film.
The transparent and electrically conductive film of the present invention 15 forming touch panel 23 is configured on display floater 31 across air layer 9, and the low-index layer 4 of transparent and electrically conductive film 15 of the present invention contacts with air layer 9.
For the display unit possessing capacitive touch panels shown in Fig. 2 and Fig. 3, be usually configured with not shown protection panel (glass plate or acrylic acid resin plate etc.) in touch side, face across not shown air layer or adhesive phase.
As mentioned above, when having the touch panel of transparent and electrically conductive film of the present invention to be assembled on the display floater of display unit use, preferably to make the low-index layer side of transparent and electrically conductive film of the present invention configure across the mode that air layer is relative with display floater.
As mentioned above, preferably transparent and electrically conductive film of the present invention is assembled in inside instead of the touch face of the display unit possessing touch panel.By transparent and electrically conductive film of the present invention being used for the inside of display unit, in marresistance, the formation (not there is hard conating or high refractive index layer) of only one deck low-index layer can be realized.
In addition, as other purposes of transparent and electrically conductive film of the present invention, the electromagnetic electromagnetic wave shielding component covering and produced by display panels can be enumerated.That is, transparent and electrically conductive film of the present invention is suitable for electromagnetic wave shielding component.
Fig. 4 possesses the generalized section using and have an example of the display unit of the electromagnetic wave shielding component of transparent and electrically conductive film of the present invention.
In the diagram, the transparent and electrically conductive film of the present invention 16 forming electromagnetic wave shielding component 24 is configured on display floater (display panels) 31 across air layer 9, and the low-index layer 4 of transparent and electrically conductive film 16 of the present invention contacts with air layer 9.For transparent and electrically conductive film 16 of the present invention, in the one side of base material film 1, there is nesa coating 2 and across easy adhesive linkage 3, only there is one deck low-index layer 4 at the another side of base material film 1.
For the display unit of Fig. 4, be configured with touch panel 25 in the side of the nesa coating 2 of the transparent and electrically conductive film of the present invention 16 of formation electromagnetic wave shielding component 24.Here, touch panel 25 is not particularly limited, also can uses the touch panel (such as ultrasonic wave mode, way of electromagnetic induction etc.) of the alternate manner beyond above-mentioned resistance membrane type or condenser type.In addition, use as above is also preferably used to have resistive touch panel or the capacitive touch panels of transparent and electrically conductive film of the present invention.
Embodiment
, in further detail the present invention is described by embodiment below, but the present invention does not limit by these embodiments.It should be noted that, the assay method in the present embodiment and evaluation method are shown below.
(1) mensuration of the refractive index of base material film
For the refractive index of base material film (PET film), measure with Abbe refractomecer according to JIS K7105 (1981).
(2) mensuration of the refractive index of easy adhesive linkage and low-index layer
For with spin coater, the respective coating composition of easy adhesive linkage and low-index layer is coated on the film (dry thickness is about 2 μm) that Silicon Wafer is formed, under the temperature conditions of 25 DEG C, the refractive index of 633nm is measured with measuring difference of phases device (Nikon Corporation manufactures, NPDM-1000).
(3) thickness of easy adhesive linkage
The section of the base material film of easy adhesive linkage is had to cut into ultra-thin section, by utilizing RuO by laminated 4dyeing, OsO 4the dyeing ultrathin sectioning of dyeing or the double staining of the two, with TEM (transmission electron microscope) observing under the following condition of visual profile construction, is measured the thickness of easy adhesive linkage by its cross sectional photograph.It should be noted that, measure 5 positions, its mean value is set as the thickness of easy adhesive linkage.
Determinator: transmission electron microscope (Hitachi, Ltd. manufactures, H-7100FA type)
Condition determination: accelerating voltage 100kV
Prepared by sample: cryoultramicrotome method
Multiplying power: 300,000 times
(4) mensuration of the thickness of low-index layer
The section of sample is cut into ultra-thin section, carry out observing (observing with the multiplying power of 100,000 times) with accelerating voltage 100kV with transmission electron microscope (the H-7100FA type that Hitachi manufactures), measured the thickness of low-index layer by its cross sectional photograph.It should be noted that, measure 5 positions, its mean value is set as the thickness of low-index layer.
(5) mensuration of the visual reflection rate of transparent and electrically conductive film
The making > of < sample for evaluation
With adhesive pasting sample on a glass with the laminated face having the side of low-index layer contrary, (day, east electrician manufactured to paste black tape at the reverse side (with the face of opposition side, face being pasted with transparent conductivity membrane sample) of this glass plate, No.21Toku (BC)), make sample for evaluation.
< measures >
Use spectrophotometer (Shimadzu Seisakusho Ltd.'s manufacture, UV3150PC), be the incidence angle of 5 degree to count from mensuration face, in the scope of wavelength 380 ~ 780nm, computational reflect rate (one side reflection), obtains visual reflection rate (the values Y of the reflection specified in JIS Z8701-1999).Use spectrophotometric determination spectrum, according to JIS Z8701-1999 computational reflect rate (machine glazing line reflection).Calculating formula is as described below.
T=K ∫ S (λ) y (λ) R (λ) d λ (wherein, integrating range is 380 ~ 780nm)
T: one side light reflectance
S (λ): for the distribution of the standard light of color display
Y (λ): the isochrome function in XYZ display system
R (λ): spectral reflectivity (spectral reflectance factor).
The standard > of < visual reflection rate
Have use have in the display unit of the touch panel of transparent and electrically conductive film of the present invention, in order to not make the transmitance from the light of display floater reduce, the visual reflection rate of the low-index layer side of transparent and electrically conductive film is preferably less than 1.0%, is more preferably less than 0.9%, is particularly preferably less than 0.8%.If visual reflection rate is greater than 1.0%, then transmitance reduces.
(6) adaptation
Each sample is placed 500 hours under the atmosphere of 60 DEG C of-90%RH, then, the film aspect of each sample draws 100 1mm 2draw lattice, thereon paste Nichiban Co., Ltd. manufacture cellophane tape, with finger energetically pressing after, peel off rapidly along 90 degree directions, by remain number, by following benchmark evaluation adaptation.
More than zero: 90/100 (residual number/mensuration number)
×: be less than 90/100 (residual number/mensuration number)
(7) sliding
Each sample is cut off and makes 2 thin slices (20cm × 15cm).To make the low-refraction aspect of 2 thin slices mode relative each other 2 thin slices to be staggered slightly and overlapping, be placed on level and smooth platform, with finger, the thin slice of below is fixed on platform, is carried out the judgement of sliding quality by the method making with hand the thin slice of top slide.Measuring environment is 23 DEG C, 55%RH.
Zero: the sliding of the thin slice of top is good.
△: the sliding of the thin slice of top is poor, but be better.
×: the thin slice of top does not slide.
(8) mensuration of the average grain diameter of the particle easily contained by adhesive linkage
For easy adhesive linkage surface, observe with the multiplying power of 10,000 times with SEM (scanning electron microscope), the image (light caused by particle deep or light) of particle is sent to image analyzer (QTM900 that such as Cambridge Instrument manufactures), change look-out station and read data, carry out following numerical value process when total population is more than 5000, the several average diameter d obtained thus are set as average grain diameter (diameter).
·d＝Σdi/N
Here, di is the equivalent diameter (having the diameter of a circle of the area identical with the sectional area of particle) of particle, and N is number.
(9) evaluation of the effect suppressing oligomer to be separated out
Each sample is placed in the baking oven of 140 DEG C, heat-treats 80 minutes.Based on JISK7105 (1981), the nephelometer NDH2000 using Japanese electricity Se Industrial Co., Ltd to manufacture measures the haze value before and after heat treatment.Based on the change of the haze value before and after heat treatment, the effect suppressing oligomer to be separated out with following benchmark evaluation.
Zero: the haze value change before and after heat treatment is less than 0.5%
△: the haze value before and after heat treatment is changed to more than 0.5% and is less than 1.0%
×: the haze value before and after heat treatment is changed to more than 1.0%.
(resin for the formation of easy adhesive linkage)
< mylar 1,2 >
By regulating the content of the fluorenes ring in mylar, the mylar 2 of preparation refractive index to be the mylar 1 of the water dispersible of 1.64 and refractive index the be water dispersible of 1.62.Namely, contain in the synthesis of fluorenes ring mylar following, by regulating ratio of components x % by mole of two for 9,9-[4-(2-hydroxyl-oxethyl) phenyl] fluorenes in the scope of 35 % by mole ~ 45 % by mole, obtain above-mentioned mylar 1 and mylar 2.
< is containing fluorenes ring mylar >
For being made up of the mylar formed the copolymerization of following carboxylic acid composition and diol component.
Carboxylic acid composition
Butanedioic acid 40 % by mole
M-phthalic acid 5-sodium sulfonate 10 % by mole
Diol component
Two [4-(2-hydroxyl-oxethyl) phenyl] the fluorenes x % by mole of 9,9-
Ethylene glycol (50-x) % by mole.
< mylar 3 >
Prepare the mylar 3 (containing naphthalene nucleus mylar) that following refractive index is the water dispersible of 1.58.
< is containing naphthalene nucleus mylar >
For being made up of the mylar formed the copolymerization of following carboxylic acid composition and diol component.
Carboxylic acid composition
Terephthalic acid (TPA) 35 % by mole
NDA 9 % by mole
M-phthalic acid 5-sodium sulfonate 6 % by mole
Diol component
Ethylene glycol 49 % by mole
Diethylene glycol (DEG) 1 % by mole.
< acrylic resin 1,2 >
Prepare the acrylic resin 2 that acrylic resin 1 that following refractive index is the water dispersible of 1.54 and refractive index are the water dispersible of 1.52 respectively.
< acrylic resin 1 >
For being made up of the acrylic resin formed following copolymerization.
Copolymer composition
< acrylic resin 2 >
For being made up of the acrylic resin formed following copolymerization.
Copolymer composition
(particle contained by easy adhesive linkage)
Particle A: average grain diameter is the cataloid of 190nm
Particle B: average grain diameter is the cataloid of 80nm
Particle C: average grain diameter is the cataloid of 30nm.
[Production Example 1]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage A makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.64.This easy adhesive linkage satisfies condition 1.
In addition, dry thickness is made to be 90nm at the laminated following easy adhesive linkage Z of the another side (face of the side of laminated nesa coating) of PET film.
< easy adhesive linkage A >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 1,5 mass parts, the particle A of 2 mass parts of 1.64.The content of each composition is the content converted in solid state component, and the following examples too.
Above-mentioned melamine series crosslinking agent is methylol type melamine series crosslinking agent (SanwaChemical Co., Ltd. " the NIKALAC MW12LF " that manufacture), in embodiment below and comparative example, melamine series crosslinking agent refers to above-claimed cpd.
< easy adhesive linkage Z >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 3,5 mass parts, the particle A of 2 mass parts of 1.58.
[Production Example 2]
Be 1.65 and the laminated following easy adhesive linkage B of one side (face of laminated low-index layer) that thickness is the PETG film (PET film) of 100 μm makes dry thickness be 20nm in refractive index, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 20nm, and the refractive index of easy adhesive linkage is 1.64.This easy adhesive linkage satisfies condition 1 and condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage B >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 1,5 mass parts, the particle B of 2 mass parts of 1.64.
[Production Example 3]
Be 1.65 and the laminated following easy adhesive linkage C of one side (face of laminated low-index layer) that thickness is the PETG film (PET film) of 100 μm makes dry thickness be 90nm in refractive index, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.62.This easy adhesive linkage satisfies condition 1.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage C >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 2,5 mass parts, the particle A of 2 mass parts of 1.62.
[Production Example 4]
Be 1.65 and the laminated following easy bonding layer D of one side (face of laminated low-index layer) that thickness is the PETG film (PET film) of 100 μm makes dry thickness be 30nm in refractive index, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 30nm, and the refractive index of easy adhesive linkage is 1.62.This easy adhesive linkage satisfies condition 1 and condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
The easy bonding layer D > of <
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 2,5 mass parts, the particle B of 2 mass parts of 1.62.
[Production Example 5]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage E makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.58.This easy adhesive linkage satisfies condition 1.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage E >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 3,5 mass parts, the particle A of 2 mass parts of 1.58.
[Production Example 6]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage F makes dry thickness be 40nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 40nm, and the refractive index of easy adhesive linkage is 1.58.This easy adhesive linkage satisfies condition 1 and condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage F >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of mylar 3,5 mass parts, the particle B of 2 mass parts of 1.58.
[Production Example 7]
Except the thickness of the easy adhesive linkage F by Production Example 6 changes to except 20nm, to operate equally with Production Example 6, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 20nm, and the refractive index of easy adhesive linkage is 1.58.This easy adhesive linkage satisfies condition 1 and condition 2.
[Production Example 8]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage G makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.54.This easy adhesive linkage neither satisfies condition and 1 does not also satisfy condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage G >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of acrylic resin 1,5 mass parts, the particle A of 2 mass parts of 1.54.
[Production Example 9]
Except the thickness of the easy adhesive linkage G by Production Example 8 changes to except 60nm, to operate equally with Production Example 8, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 60nm, and the refractive index of easy adhesive linkage is 1.54.This easy adhesive linkage neither satisfies condition and 1 does not also satisfy condition 2.
[Production Example 10]
Except the thickness of the easy adhesive linkage G by Production Example 8 changes to except 40nm, to operate equally with Production Example 8, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 40nm, and the refractive index of easy adhesive linkage is 1.54.This easy adhesive linkage satisfies condition 2.
[Production Example 11]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage H makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.52.This easy adhesive linkage neither satisfies condition and 1 does not also satisfy condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage H >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of acrylic resin 2,5 mass parts, the particle A of 2 mass parts of 1.52.
[Production Example 12]
Except the thickness of the easy adhesive linkage H by Production Example 11 changes to except 60nm, to operate equally with Production Example 11, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 60nm, and the refractive index of easy adhesive linkage is 1.52.This easy adhesive linkage neither satisfies condition and 1 does not also satisfy condition 2.
[Production Example 13]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage I makes dry thickness be 20nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 20nm, and the refractive index of easy adhesive linkage is 1.52.This easy adhesive linkage satisfies condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage I >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of acrylic resin 2,5 mass parts, the particle B of 2 mass parts of 1.52.
[Production Example 14]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage J makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.52.This easy adhesive linkage neither satisfies condition and 1 does not also satisfy condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage J >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of acrylic resin 2,5 mass parts, the particle C of 2 mass parts of 1.52.
[Production Example 15]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage K makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.52.This easy adhesive linkage neither satisfies condition and 1 does not also satisfy condition 2.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage K >
Refractive index containing 100 mass parts is the melamine series crosslinking agent of acrylic resin 2,5 mass parts of 1.52.This easy adhesive linkage F is the easy adhesive linkage not containing particle.
[Production Example 16]
Prepare the PET film (refractive index be 1.65, thickness be 100 μm) of not laminated easy adhesive linkage.
[Production Example 17-1]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage L makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.60.This easy adhesive linkage satisfies condition 1.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage L >
The zirconia (average grain diameter is 20nm) of mylar 3,20 mass parts containing 100 mass parts, the melamine series crosslinking agent of 15 mass parts, the particle A of 1 mass parts.
[Production Example 17-2]
In above-mentioned Production Example 17-1, except the dry thickness of easy adhesive linkage L is changed to except 120nm, to operate equally with Production Example 17-1, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 120nm, and the refractive index of easy adhesive linkage is 1.60.This easy adhesive linkage satisfies condition 1.
[Production Example 17-3]
In above-mentioned Production Example 17-1, except the dry thickness of easy adhesive linkage L is changed to except 150nm, to operate equally with Production Example 17-1, obtain the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 150nm, and the refractive index of easy adhesive linkage is 1.60.This easy adhesive linkage satisfies condition 1.
[Production Example 18]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage M makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.65.This easy adhesive linkage satisfies condition 1.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage M >
The zirconia (average grain diameter is 20nm) of mylar 3,60 mass parts containing 100 mass parts, the melamine series crosslinking agent of 15 mass parts, the particle A of 1 mass parts.
[Production Example 19]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, laminated following easy adhesive linkage N makes dry thickness be 90nm, obtains the PET film with easy adhesive linkage.
The thickness of the easy adhesive linkage of the PET film of the easy adhesive linkage of above-mentioned obtained band is 90nm, and the refractive index of easy adhesive linkage is 1.66.This easy adhesive linkage satisfies condition 1.
In addition, at the another side (face of the side of laminated nesa coating) of PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< easy adhesive linkage N >
The zirconia (average grain diameter is 20nm) of mylar 3,67 mass parts containing 100 mass parts, the melamine series crosslinking agent of 15 mass parts, the particle A of 1 mass parts.
[Production Example 20]
Be 1.65 and thickness is the one side (face of laminated low-index layer) of the PETG film (PET film) of 100 μm in refractive index, replace easy adhesive linkage, with the high refractive index layer of the laminated following active energy ray-curable (ultra-violet solidified) of the mode making dry thickness be 90nm and irradiation ultraviolet radiation, obtain the laminated PET film having high refractive index layer.
Above-mentioned obtained laminatedly have the thickness of the high refractive index layer of the PET film of high refractive index layer to be 90nm, and the refractive index of high refractive index layer is 1.65.
In addition, at the another side (face of the side of laminated nesa coating) of above-mentioned PET film, laminated easy adhesive linkage Z makes dry thickness be 90nm in the same manner as Production Example 1.
< high refractive index layer >
The zirconia (average grain diameter is 20nm) of the dipentaerythritol acrylate as active energy ray-curable resin containing 100 mass parts, 100 mass parts and the Photoepolymerizationinitiater initiater (" Irgacure (registered trade mark) 184 " that Ciba Specialty Chemicals Ltd. manufactures) of 5 mass parts.
[embodiment 1 ~ 33 and comparative example 1 ~ 25]
According to following main points, make the transparent and electrically conductive film of embodiment 1 ~ 33 and comparative example 1 ~ 25.
The surface of an easy adhesive linkage (the easy adhesive linkage of the side of laminated low-index layer) of the PET film of the easy adhesive linkage of band obtained in above-mentioned Production Example 1 ~ 19, forms following low-index layer A, low-index layer B, low-index layer C or low-index layer D.In addition, on the laminated high refractive index layer having the PET film of high refractive index layer that above-mentioned Production Example 20 obtains, form low-index layer C.
The band PET film of easy adhesive linkage and the combination of low-index layer are shown in table 1 ~ table 3.
In addition, on the surface of another easy adhesive linkage (the easy adhesive linkage of transparency conducting layer side) of the PET film of the easy adhesive linkage of band, laminated following hard conating, high refractive index layer, SiO successively 2film and nesa coating, make transparent and electrically conductive film.
< low-index layer A >
Make 47 mass parts active energy ray-curable resins (containing dipentaerythritol acrylate and urethane acrylate with mass ratio 1:3), the hollow silica (ELECOM-P5024 that RiHui catalyst synthesis Co., Ltd manufactures) of 50 mass parts is counted with solid state component, the polysiloxane compound (" X-22-164C " that Shin-Etsu Chemial Co., Ltd manufactures) with ethylenic unsaturated group of 3 mass parts and 3 mass parts Photoepolymerizationinitiater initiaters (" Irgacure (registered trade mark) 184 " that Ciba Specialty Chemicals Ltd. manufactures) disperse or dissolve in organic solvent, prepare active energy line curing resin composition.The refractive index of said composition is 1.35.
Said composition is coated with by wet coating method (gravure coating process), and at 90 DEG C after drying, with 400mJ/cm 2irradiation ultraviolet radiation makes it solidify, and forms low-index layer.For the thickness (thickness after solidification) of low-index layer, as shown in Table 1 to Table 3, it is made to change between 70nm, 90nm, 100nm, 110nm, 130nm.
< low-index layer B >
Make the active energy ray-curable resin of 59 mass parts (containing dipentaerythritol acrylate and urethane acrylate with mass ratio 1:3), the hollow silica (ELECOM-P5024 that RiHui catalyst synthesis Co., Ltd manufactures) of 38 mass parts is counted with solid state component, the polysiloxane compound (" X-22-164C " that Shin-Etsu Chemial Co., Ltd manufactures) with ethylenic unsaturated group of 3 mass parts and 3 mass parts Photoepolymerizationinitiater initiaters (" Irgacure (registered trade mark) 184 " that Ciba Specialty Chemicals Ltd. manufactures) disperse or dissolve in organic solvent, prepare active energy line curing resin composition.The refractive index of said composition is 1.38.
Said composition is coated with by wet coating method (gravure coating process), and at 90 DEG C after drying, with 400mJ/cm 2irradiation ultraviolet radiation makes it solidify, and forms low-index layer.For the thickness (thickness after solidification) of low-index layer, as shown in Table 1 to Table 3, it is made to change between 90nm, 100nm, 110nm.
< low-index layer C >
Make 67 mass parts active energy ray-curable resins (containing dipentaerythritol acrylate and urethane acrylate with mass ratio 1:3), the hollow silica (ELECOM-P5024 that RiHui catalyst synthesis Co., Ltd manufactures) of 30 mass parts is counted with solid state component, 3 mass parts have polysiloxane compound (" X-22-164C " that Shin-Etsu Chemial Co., Ltd manufactures) and 3 mass parts Photoepolymerizationinitiater initiaters (" Irgacure (registered trade mark) 184 " that the Ciba Specialty Chemicals Ltd. manufactures) dispersion of ethylenic unsaturated group or dissolve in organic solvent, prepare active energy line curing resin composition.The refractive index of said composition is 1.40.
Said composition is coated with by wet coating method (gravure coating process), and at 90 DEG C after drying, with 400mJ/cm 2irradiation ultraviolet radiation makes it solidify, and forming thickness is the low-index layer of 100nm.
< low-index layer D >
Make 82 mass parts active energy ray-curable resins (containing dipentaerythritol acrylate and urethane acrylate with mass ratio 1:3), count the hollow silica of 15 mass parts (ELECOM-P5024 that RiHui catalyst synthesis Co., Ltd manufactures) and 3 mass parts Photoepolymerizationinitiater initiaters (" Irgacure (registered trade mark) 184 " of Ciba Specialty Chemicals Ltd. manufacture) disperse or dissolve in organic solvent with solid state component, prepare active energy line curing resin composition.The refractive index of said composition is 1.43.
Said composition is coated with by wet coating method (gravure coating process), and at 90 DEG C after drying, with 400mJ/cm 2irradiation ultraviolet radiation makes it solidify, and forming thickness is the low-index layer of 100nm.
< hard conating >
Preparation comprises the composition of 95 mass parts active energy ray-curable resins (containing dipentaerythritol acrylate and urethane acrylate with mass ratio 1:3), 5 mass parts Photoepolymerizationinitiater initiaters (" Irgacure (registered trade mark) 184 " that Ciba Specialty Chemicals Ltd. manufactures).The refractive index of said composition is 1.50.
Said composition is coated with by wet coating method (gravure coating process), and at 90 DEG C after drying, with 400mJ/cm 2irradiation ultraviolet radiation makes it solidify, and forms the hard conating that thickness is 2 μm.
< high refractive index layer >
Make 37 mass parts active energy ray-curable resins (dipentaerythritol acrylate 10 mass parts and urethane acrylate 27 mass parts), 60 mass parts zirconias (average grain diameter is 20nm) and 3 mass parts Photoepolymerizationinitiater initiaters (" Irgacure (registered trade mark) 184 " that Ciba Specialty ChemicalsLtd. manufactures) dispersion or dissolve in organic solvent, preparing composition.The refractive index of said composition is 1.70.
Said composition is coated with by wet coating method (gravure coating process), and at 90 DEG C after drying, with 400mJ/cm 2irradiation ultraviolet radiation makes it solidify, and forming thickness is the high refractive index layer of 80nm.
< SiO 2film >
By the laminated SiO of sputtering method 2film (refractive index is 1.46) makes thickness be 10nm.
< nesa coating >
Make thickness be 30nm by the laminated ito film of sputtering method, and carry out pattern processing (etch processes), form nesa coating.
[evaluation of transparent and electrically conductive film]
For the transparent and electrically conductive film of above-mentioned obtained embodiment and comparative example, evaluate visual reflection rate, adaptation and sliding.These results evaluated are shown in table 1 ~ table 3.
From the result of table 1 ~ table 3, the visual reflection rate of embodiments of the invention is little, and the adaptation of low-index layer and sliding good.
The easy adhesive linkage of the easy adhesive linkage PET film that comparative example 1 ~ 6,8,9 uses neither satisfies condition and 1 does not also satisfy condition 2, and therefore, visual reflection rate becomes large.
In addition, although the easy adhesive linkage of the easy adhesive linkage PET film of comparative example 5 contains particle, the average grain diameter (r) of particle is less than 0.5 relative to the ratio (r/d) of the thickness (d) of easy adhesive linkage, and therefore, sliding is poor.The easy adhesive linkage of the easy adhesive linkage PET film of comparative example 6 is not containing particle, and therefore, sliding is poor.Have the comparative example 7 of the PET film without easy adhesive linkage for using, adaptation and sliding poor.
For comparative example 10 ~ 14,15,16, the refractive index of low-index layer is more than 1.42, and visual reflection rate becomes large.In addition, the low-index layer D of comparative example 10 ~ 14,15,16 is not containing the polysiloxane compound with ethylenic unsaturated group, therefore, compared with low-index layer A, B, C of comprising the polysiloxane compound with ethylenic unsaturated group, sliding is poor.
In addition, the easy adhesive linkage of the easy adhesive linkage PET film of comparative example 14 is not containing particle, and use has the low-index layer D not comprising the polysiloxane compound with ethylenic unsaturated group, and therefore, sliding is poor.From these results, comprising the particle of appropriate size by making easy adhesive linkage and low-index layer comprises the polysiloxane compound with ethylenic unsaturated group, good sliding can be obtained.
For comparative example 17 ~ 20, the thickness of low-index layer is less than 80nm, and therefore, visual reflection rate becomes large, and in addition, the effect suppressing oligomer to be separated out also reduces.
For comparative example 21 ~ 24, the thickness of low-index layer is more than 120nm, and therefore, visual reflection rate becomes large.
For comparative example 25, although the high refractive index layer being provided with active energy ray-curable replaces easy adhesive linkage, poor with the adaptation of base material film.
Symbol description
1,5: base material film
2,6: nesa coating
3: easily adhesive linkage
4: low-index layer
7: functional layer
8: spacer
9: air layer
11,13,14,15,16: transparent and electrically conductive film of the present invention
12: transparent and electrically conductive film
21,22,23,25: touch panel
24: electromagnetic wave shielding component
31: display floater

Claims (16)

1. a transparent and electrically conductive film, it is characterized in that, be that the one side of the base material film of 1.6 ~ 1.7 has nesa coating in refractive index, across easy adhesive linkage, only there is one deck refractive index at the another side of described base material film and be less than 1.42 and thickness is the low-index layer of 80 ~ 120nm, described easy adhesive linkage is not the resin bed be cured by active energy ray, and described easy adhesive linkage meets following condition 1
Condition 1: the absolute value of the refractive index of base material film and the specific refractivity of easy adhesive linkage is less than 0.08.
2. a transparent and electrically conductive film, it is characterized in that, be that the one side of the base material film of 1.6 ~ 1.7 has nesa coating in refractive index, across easy adhesive linkage, only there is one deck refractive index at the another side of described base material film and be less than 1.42 and thickness is the low-index layer of 80 ~ 120nm, described easy adhesive linkage is not the resin bed be cured by active energy ray, and described easy adhesive linkage meets following condition 2
Condition 2: easily the thickness of adhesive linkage is more than 5nm and is less than 50nm.
3. a transparent and electrically conductive film, it is characterized in that, be that the one side of the base material film of 1.6 ~ 1.7 has nesa coating in refractive index, across easy adhesive linkage, only there is one deck refractive index at the another side of described base material film and be less than 1.42 and thickness is the low-index layer of 80 ~ 120nm, described easy adhesive linkage is not the resin bed be cured by active energy ray, and described easy adhesive linkage meets following condition 1 and condition 2
Condition 1: the absolute value of the refractive index of base material film and the specific refractivity of easy adhesive linkage is less than 0.08;
Condition 2: easily the thickness of adhesive linkage is more than 5nm and is less than 50nm.
4. the transparent and electrically conductive film as described in claim 1 or 3, wherein, the absolute value of the refractive index of described base material film and the specific refractivity of easy adhesive linkage is less than 0.05.
5. transparent and electrically conductive film as claimed in claim 1, wherein, the thickness of described easy adhesive linkage is more than 5nm and is less than 200nm.
6. the transparent and electrically conductive film according to any one of claims 1 to 3, wherein, described easy adhesive linkage is through heat treated layer.
7. the transparent and electrically conductive film according to any one of claims 1 to 3, wherein, described base material film is polyester film, and described polyester film is PETG film.
8. the transparent and electrically conductive film according to any one of claims 1 to 3, wherein, described easy adhesive linkage is at least containing resin and crosslinking agent, and described crosslinking agent is selected from melamine series crosslinking agent, oxazoline system crosslinking agent, carbodiimide system crosslinking agent, isocyanate-based crosslinking agent, aziridine system crosslinking agent, epoxy crosslinking agent, in methylolation or alkanolized urea system crosslinking agent, acrylamide crosslinking agent, polyamide series resin, amide epoxy compound, various silane coupler, various titanate esters systems coupling agent at least a kind.
9. transparent and electrically conductive film as claimed in claim 8, wherein, described resin is mylar.
10. the transparent and electrically conductive film according to any one of claims 1 to 3, wherein, described low-index layer is by the coat activated energy line curing resin composition of wet coating method and the layer making it solidify.
11. transparent and electrically conductive films according to any one of claims 1 to 3, wherein, described easy adhesive linkage comprises particle, and the average grain diameter (r) of described particle meets following formula 1 with the relation of the thickness (d) of easy adhesive linkage,
0.5≤(r/d)≤20 ... formula 1.
12. transparent and electrically conductive films as claimed in claim 11, wherein, relative to the solid state component total amount 100 quality % of described easy adhesive linkage, the described particle containing 0.05 ~ 20 quality %.
13. transparent and electrically conductive films according to any one of claims 1 to 3, wherein, described low-index layer contains the polysiloxane compound with ethylenic unsaturated group.
14. 1 kinds of touch panels, it possesses the transparent and electrically conductive film according to any one of claim 1 ~ 13.
15. 1 kinds of display unit, it is the display unit being configured with the touch panel using the transparent and electrically conductive film of having the right according to any one of requirement 1 ~ 13 on a display panel, and described display unit configures across the mode that air layer is relative with display floater with the described low-index layer side of described transparent and electrically conductive film.
16. 1 kinds of display unit, it is the display unit being configured with the electromagnetic wave shielding component using the transparent and electrically conductive film of having the right according to any one of requirement 1 ~ 13 on a display panel, and described display unit configures across the mode that air layer is relative with display floater with the described low-index layer side of described transparent and electrically conductive film.
CN201380006513.7A 2012-01-31 2013-01-16 Transparent conductive film, touch panel, and display device Expired - Fee Related CN104067352B (en)

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