CN104656974B - Conductive film, hard coat film and contact panel sensor - Google Patents

Conductive film, hard coat film and contact panel sensor Download PDF

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Publication number
CN104656974B
CN104656974B CN201410662938.XA CN201410662938A CN104656974B CN 104656974 B CN104656974 B CN 104656974B CN 201410662938 A CN201410662938 A CN 201410662938A CN 104656974 B CN104656974 B CN 104656974B
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Prior art keywords
refractive index
index layer
layer
mentioned
low
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CN104656974A (en
Inventor
小川善正
中川博喜
芳片邦聪
大川晃次郎
黑田刚志
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP2014055419A external-priority patent/JP5549967B1/en
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to CN201611088984.9A priority Critical patent/CN107153478A/en
Priority to CN201810521529.6A priority patent/CN108733262A/en
Publication of CN104656974A publication Critical patent/CN104656974A/en
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    • 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
    • G06F3/0412—Digitisers structurally integrated in a display
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

The present invention provides conductive film, dura mater and contact panel sensor.Inhibit the fluctuation of tone in the case where with the viewing of various angles.Hard coat film lubricity is excellent and can be realized the low resistance value of the conductive layer when forming conductive layer.Patterned conductive film (10) includes Mght-transmitting base material (11), lamination is in the high refractive index layer (14) in the one or two sides of Mght-transmitting base material (11), lamination is in the low-index layer (15) on high refractive index layer (14), lamination is on low-index layer (15) and patterned transparency conducting layer (16), the surface (16A) of transparency conducting layer (16) forms the surface (10A) of conductive film (10), by lateral transparency conducting layer (16) irradiation light in the surface (16A) of transparency conducting layer (16), and set conductive film (10) surface (10A) normal direction as 0 °, every 5 degree incident angle is converted in 5 ° or more 75 ° or less of range to be irradiated, L*a* is found out by the respective reflected light towards mirror-reflection direction When the a* value and b* value of b* colorimeter system, the fluctuation of a* value is within 3.5, and the fluctuation of b* value is within 7.0.

Description

Conductive film, hard coat film and contact panel sensor
[technical field]
The present invention relates to conductive film, hard coat film and contact panel sensors.
[background technique]
Nowadays touch control panel device is widely used as input medium.Touch control panel device have contact panel sensor, Control circuit, wiring and the FPC (flexible print substrates) that contact position in contact panel sensor is detected.It is most In the case of, touch control panel device is as the various dresses for installation to the display devices such as liquid crystal display, plasma display The input medium and display device for setting etc. (such as ticket machine, ATM device, mobile phone, game machine) are used together.Such dress In setting, contact panel sensor is configured on the display surface of the display device, extremely direct thus, it is possible to carry out for display device Input.
Touch control panel device is based on the principle detected to the contact position (leaning near position) in contact panel sensor And it is divided into various forms.So far, for optically becoming clear, have the function of that aesthetics, structure be easy, the reasons such as excellent, direct capacitance The touch control panel device of amount mode attracts attention.Electrostatic capacity has surface type and projection type, due to being suitable for reply multiconductor It identifies (multiple spot identification), projection type is concerned.
As the contact panel sensor of the touch panel for projection type electrostatic capacity, has and have by intermediate base material The contact panel sensor for the conductive film that film, the transparency conducting layer being formed on the intermediate substrate film are constituted is (for example, see patent Document 1).
As the transparent and electrically conductive film for contact panel sensor, it is known in the translucency formed by high molecular material The composition for the conductive layer being made of conductive metal oxides such as ITO is formed on substrate, in turn, from preventing due to from translucency Substrate is precipitated from the aspect of the deterioration of the transparency caused by the low molecular weight compositions such as oligomer, in Mght-transmitting base material and conduction Curing resin layer (priming coat) is formed between layer (such as to join to prevent the technology of the diffusion of low molecular weight compositions to be well-known See patent document 2 etc.).
Also, as the existing transparent and electrically conductive film for contact panel sensor, it is also known that Mght-transmitting base material with It is laminated with high refractive index layer and low-index layer between conductive layer, realizes the sightless composition of conductive layer (for example, see special Sharp document 3).
[existing technical literature]
[patent document]
Patent document 1: Japanese Unexamined Patent Publication 2011-98563 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-103504 bulletin
Patent document 3: Japanese Patent No. 4661995
[summary of the invention]
[problems to be solved by the invention]
Now, it is pushing forward the enlargement of touch panel devices, along with the larger in area of touch control panel device, picture It becomes large-sized, there is the tendency to differ widely according to the position difference viewing angle of viewing touch control panel device.Touch panel dress The conductive film of contact panel sensor used in setting is to design take the front view as a precondition, this with from front Under design philosophy premised on viewing, tone can be fluctuated under certain viewing angles, it is therefore possible to can not cope with touch panel Device it is larger in area.
Present invention is proposed to solve the above problem.That is, the 1st is designed to provide and can be seen with various angles Inhibit the conductive film and contact panel sensor of the fluctuation of tone in the case where seeing.
In addition, there are the profits of the conductive layer on surface for transparent conductivity laminate used in existing contact panel sensor Slip is insufficient, the poor such problems of adhesion resistance；The resistance value of conductive layer gets higher such problems.
In view of this point, the present invention the 2nd is designed to provide hard coat film and the touch panel sensing with the hard coat film Device while lubricity is excellent, can be realized the low resistance value of the conductive layer when forming conductive layer.
[means to solve the problem]
1st mode according to the present invention, provides a kind of conductive film, includes Mght-transmitting base material, lamination in the light transmission Property substrate one or two sides on high refractive index layer, lamination is on the high refractive index layer and refractive index is lower than the high refraction The low-index layer of the refractive index of rate layer, lamination are on the low-index layer and patterned transparency conducting layer, by described Transparency conducting layer irradiation light described in the surface lateral of transparency conducting layer, and set the normal to a surface direction of the conductive film as 0 °, every 5 degree incident angle is converted in 5 ° or more 75 ° or less of range and is irradiated, by respective towards mirror-reflection side To reflected light find out the a* value and b* value of L*a*b* colorimeter system when, the fluctuation of a* value is within 3.5, and the fluctuation of b* value is Within 7.0.
The other modes of 1st mode according to the present invention, provide the contact panel sensor with above-mentioned conductive film.
2nd mode according to the present invention, provides a kind of hard coat film, is that primary coat is successively laminated on Mght-transmitting base material The hard coat film of layer, high refractive index layer and low-index layer, which is characterized in that above-mentioned low-index layer has concave-convex on surface Shape is measuring the concaveconvex shape for the above-mentioned low-index layer that 0.12mm in the visual field is measured using sweep type white Gan Wataru microscope The value of 10 mean roughness and arithmetic average roughness, which is all larger than, to be surveyed using scanning type probe microscope in 5 μm of the visual field of measurement The value of 10 mean roughness and arithmetic average roughness of the concaveconvex shape of fixed above-mentioned low-index layer.
The other modes of 2nd mode according to the present invention, provide the contact panel sensor with hard coat film.
[The effect of invention]
The conductive film and contact panel sensor of 1st mode according to the present invention can watched with various angles In the case of inhibit tone fluctuation.
Also, the adhesion resistance and lubricity of the hard coat film of the 2nd mode of the invention are excellent, while can be realized conductive layer Low resistance value.Therefore, the hard coat film of the 2nd mode of the invention can suitably be applied to contact panel sensor, especially It is the contact panel sensor of electrostatic capacity.
[Detailed description of the invention]
Fig. 1 is the schematic constitution diagram of the conductive film of the 1st embodiment of the 1st mode of the invention.
Fig. 2 is the top view of a part of patterned transparency conducting layer.
Fig. 3 is the schematic diagram shown using a* and b* of the spectrophotometer to the conductive film state being measured.
Fig. 4 is the schematic constitution diagram of the contact panel sensor of the 1st embodiment of the 1st mode of the invention.
Fig. 5 is the vertical view of the Sensor section of the contact panel sensor of the 1st embodiment of the 1st mode of the invention Figure.
Fig. 6 is the schematic composition of other contact panel sensors of the 1st embodiment of the 1st mode of the invention Figure.
Fig. 7 is the schematic constitution diagram of the conductive film of the 2nd embodiment of the 1st mode of the invention.
Fig. 8 is the schematic constitution diagram of the contact panel sensor of the 2nd embodiment of the 1st mode of the invention.
Fig. 9 is the schematic constitution diagram of the conductive film of the 3rd embodiment of the 1st mode of the invention.
Figure 10 is the schematic constitution diagram of other conductive films of the 3rd embodiment of the 1st mode of the invention.
[specific embodiment]
(the 1st mode of the invention)
[the 1st embodiment]
The conductive film and contact panel sensor of the 1st embodiment of the invention are illustrated referring to the drawings. Fig. 1 is the schematic constitution diagram of the conductive film of present embodiment, and Fig. 2 is bowing for a part of patterned transparency conducting layer View, Fig. 3 are the signals for showing the state being measured using spectral reflectance of the spectral reflectance determiner to conductive film Figure.It should be noted that the terms such as " film ", " piece ", " plate " are only address differences, and not different from each other in this specification. Thus, for example, also including the component that can be referred to piece or plate in the concept of " film ".As a concrete example, in " conductive film " It also include the component referred to as " conductive sheet " etc..
<<conductive film>>
Conductive film be have Mght-transmitting base material, lamination in the one or two sides of Mght-transmitting base material high refractive index layer, Lamination on high refractive index layer and refractive index lower than the low-index layer of refractive index of high refractive index layer, lamination in low-index layer Upper and patterned transparency conducting layer.Also, also by above-mentioned with Mght-transmitting base material, high refractive index layer and low-index layer Film is referred to as " intermediate base material film ".So-called " intermediate base material film ", such as be installed in the case that the devices such as touch panel carry out use, Mean the outmost surface for being not intended to the devices such as touch panel but for the base material film inside the device of touch panel etc..It leads In electrical film, patterned transparency conducting layer is supported by the intermediate base material film.
Conductive film 10 shown in FIG. 1 has Mght-transmitting base material 11；The primary coat being formed on the two sides of Mght-transmitting base material 11 Layer 12,13；The high refractive index layer 14 being formed on priming coat 12；The low-index layer 15 being formed on high refractive index layer 14；With Lamination is on low-index layer 15 and patterned transparency conducting layer 16.Conductive film 10 has priming coat 12,13, but can also Not have priming coat 12 and/or priming coat 13.The surface 16A of transparency conducting layer 16 forms the surface 10A of conductive film 10.Institute Meaning " surface of transparency conducting layer " means the face of side opposite with the face of Mght-transmitting base material side in transparency conducting layer.
Fig. 2 is the top view for showing an example of patterned transparency conducting layer, and the I-I line sectional view in figure is Fig. 1.Thoroughly Bright conductive layer 16 plays a role as the electrode in X-direction in contact panel sensor 20, therefore as shown in Fig. 2, constitutes transparent The pattern form of conductive layer 16 is electrically connected in a lateral direction.As shown in Figure 1, patterned transparency conducting layer 16 is set to conduction On the low-index layer 15 of property film 10.
In conductive film 10, can have high refractive index layer 14, low-index layer 15 and transparent on the priming coat 13 Conductive layer 16.Specifically, other than conductive film 10 shown in FIG. 1, can be in following conductive film as conductive film Any one: be successively arranged priming coat, high refractive index layer, low-index layer on a face of Mght-transmitting base material and transparent lead Electric layer and the conductive film that priming coat is not provided on another face of Mght-transmitting base material；On a face of Mght-transmitting base material according to It is secondary be equipped with priming coat, high refractive index layer, low-index layer and transparency conducting layer and on another face of Mght-transmitting base material successively Conductive film equipped with priming coat and high refractive index layer；Priming coat, high refraction are successively arranged on a face of Mght-transmitting base material Rate layer, low-index layer and transparency conducting layer and priming coat, high refractive index are successively arranged on another face of Mght-transmitting base material The conductive film of layer and low-index layer；With priming coat, high refractive index layer, low is successively arranged on a face of Mght-transmitting base material Index layer and transparency conducting layer and priming coat, high refractive index layer, low folding are successively arranged on another face of Mght-transmitting base material Penetrate the conductive film of rate layer and transparency conducting layer.
In conductive film 10, visible light is irradiated by the surface lateral transparency conducting layer 16 of transparency conducting layer 16, and set conduction Property film 10 normal to a surface direction be 0 °, every 5 degree convert incident angle in 5 ° or more 75 ° or less of range and shone It penetrates, when finding out the a* value and b* value of L*a*b* colorimeter system by the respective reflected light towards mirror-reflection direction, the wave of a* value It moves and is within 3.5, and the fluctuation of b* value is within 7.0." L*a*b* colorimeter system ", " a* " and " b* " are based on JIS Z8729。
A* value and b* value are measured according to JIS Z8722, specifically, well known spectrophotometer can be used for example To find out.Spectrophotometer 100 shown in Fig. 3 has: can above 0 ° and below 75 ° in the range of move light source 101, with The movement of light source while the mobile detector 102 so as to receive the reflected light in mirror-reflection direction.Shifting for light source 101 Dynamic angle, is set as 0 ° for the normal direction N of conductive film 10.From light source 101 to 16 irradiation light of transparency conducting layer of conductive film, Receive the reflected light in mirror-reflection direction, using detector 102 so as to according to the reflection received using the detector 102 Light finds out a* value and b* value.As spectrophotometer, the absolute reflectance measurement of Japan Spectroscopy Corporation's manufacture can be enumerated Device VAR-7010 and UV, visible light near infrared spectrometer V-7100 etc..As light source, plain (WI) lamp of tungsten halogen can be enumerated It is used alone or heavy hydrogen (D2) lamp and tungsten halogen element (WI) lamp shares.Also, in the measurement, as the incident angle becomes larger, s is inclined Vibration light and the reflection differences of p-polarization light can become larger, therefore in order to accurately be measured and it is preferable to use transmission axis to tilt 45 ° Polarizer.
Fluctuation for a* value and b* value can use above-mentioned spectrophotometer and find out a* value and b* under each incident angle Value, calculates the absolute value of the difference of its maxima and minima, thus finds out the fluctuation of a* value and b* value.It is preferred that the fluctuation of a* value Within 1.5, and the fluctuation of preferably b* value is within 5.5.
For finding out the reflected light of certain angle of above-mentioned a* value and b* value and finding out the other angles of above-mentioned a* value and b* value Reflected light color difference Δ E*ab, be preferably 5 or less." Δ E*ab " is based on JIS Z8730.
<Mght-transmitting base material>
Mght-transmitting base material 11 is not particularly limited, as long as having translucency, it can be cited for example that polyolefin base material, Polycarbonate substrate, polyacrylate base material, polyester base material, aromatic polyether ketone base material, polyether sulfone substrate or polyamide-based Material.
As polyolefin base material, it can be cited for example that making so that polyethylene, polypropylene, annular polyolefin substrate etc. are at least one For the substrate of constituent.As annular polyolefin substrate, it can be cited for example that the substance with enb skeleton.
As polycarbonate substrate, it can be cited for example that aromatic copolycarbonate based on bisphenols (bisphenol A, etc.) Aliphatic polycarbonate substrates such as substrate, diethylene glycol bis-allyl carbonate etc..
As polyacrylate base material, it can be cited for example that poly(methyl) acrylate base material, poly- (methyl) acrylic acid Ethyl ester substrate, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer substrate etc..
As polyester base material, it can be cited for example that with polyethylene terephthalate (PET), poly terephthalic acid the third two Alcohol ester, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) at least one substrate for constituent.
As aromatic polyether ketone base material, it can be cited for example that polyether-ether-ketone (PEEK) substrate etc..
The thickness of Mght-transmitting base material 11 is not particularly limited, can be 5 μm or more 300 μm hereinafter, from the side such as treatability Face is set out, and the lower limit of the thickness of Mght-transmitting base material 11 is preferably 25 μm or more, and more preferably 50 μm or more.In terms of filming It sets out, the upper limit of the thickness of Mght-transmitting base material 11 is preferably 250 μm or less.
In order to improve caking property, in addition to the surface to Mght-transmitting base material 11 carries out the objects such as Corona discharge Treatment, oxidation processes Reason processing is outer, also can use the coating referred to as anchoring agent, precoating coating and is coated in advance.As anchoring agent, precoating paint, Such as polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate system resin, ethlyene dichloride-second can be used Vinyl acetate copolymer, acrylic resin, polyvinyl alcohol resin, polyvinyl acetal resin, ethylene and vinyl acetate Or acrylic acid etc. copolymer, ethylene and styrene and/or butadiene etc. the thermoplastic resins such as copolymer, olefin resin and/ Or the polymer and at least one of thermosetting resins such as epoxy resin etc. of its modified resin, photopolymerizable compound.
<priming coat>
Priming coat (also referred to as hard conating) pencil hardness test as defined in JIS K5600-5-4 (1999) (4.9N load) In with the hardness more than " H ".By making pencil hardness " H " or more, the hardness of priming coat 12 can be made fully to be reflected into The surface of transparency conducting layer 16, can be improved durability.It should be noted that from the high refractive index that is formed on priming coat 12 It the adaptation of layer 14, toughness and sets out in terms of preventing warpage, the upper limit of the pencil hardness on the surface of priming coat 12 is preferably 4H Degree.Contact panel sensor can be extruded repeatedly, it is desirable that the adaptation and toughness with height, therefore, by the bottom of by The upper limit of the pencil hardness of coating 12 is set as 4H, can by conductive film 10 be installed on contact panel sensor carry out using when Play significant effect.It, can be with to intermediate base material film also, when forming transparency conducting layer 16 on low-index layer 15 Heating, influenced by the heating, it is possible that oligomer is precipitated to make the mist of intermediate base material film by Mght-transmitting base material The problem of degree rises, but priming coat can play a role as the layer of inhibition oligomer precipitation.
Priming coat 12,13 has the refractive index lower than high refractive index layer 14.The refractive index of priming coat 12,13 is preferably 1.45 Above 1.60 or less.The lower limit of the refractive index of priming coat 12,13 is more preferably 1.48 or more, the refractive index of priming coat 12,13 The upper limit is more preferably 1.57 or less.The refractive index of priming coat 13 is not necessarily consistent with the refractive index of priming coat 12.
The refractive index of priming coat 12,13 can utilize (the Atago society manufacture of Abbe index meter after forming a separate layer NAR-4T), ellipsometer is measured.It, can benefit respectively also, as the method for being formed as measuring refractive index after conductive film 10 Lower priming coat 12,13 is cut with cutter etc., powdered sample is made, then using based on JISK7142 (2008) B method (powder Or granular transparent material with) Baker process (it is following methods:, will be described using Cargille reagent known to refractive index Powdered sample is placed on glass slide etc., and reagent is added dropwise on this sample, and sample is immersed in reagents.It is seen using microscope Its state is examined, by visual observation to the open-wire line for being different from the refractive index of the reagent due to sample and occurring in sample profile；By Becke line Refractive index of the refractive index of reagent when can not observe as sample).
It is preferred that the film thickness of priming coat 12,13, which is 0.5 μm or more,.Priming coat 12,13 with a thickness of 0.5 μm or more when, It can obtain desired hardness.The film thickness of priming coat 12,13 can be measured by cross sectional microscopy observation.The thickness of priming coat The lower limit of degree is more preferably 1.0 μm or more, and the upper limit is more preferably 7.0 μm hereinafter, the thickness of priming coat 12,13 is more preferably 1.5 μ 5.0 μm of m or more or less.The film thickness of priming coat 13 is not necessarily consistent with the film thickness of priming coat 12.
Priming coat 12,13 can be made of such as resin.Resin contains the polymer of photopolymerizable compound (cross-linking agent). In resin, solvent-dry type resin, thermosetting resin can also be contained in addition to photopolymerizable compounds of polymers (crosslinkers). Photopolymerizable compound at least has an optical polymerism functional group." optical polymerism functional group " in this specification is can to pass through The functional group of polymerization reaction occurs for light irradiation.As optical polymerism functional group it can be cited for example that (methyl) acryloyl group, ethylene The ethylenic double bonds such as base, allyl.It should be noted that in the meaning of " (methyl) acryloyl group " include " acryloyl group " and Both " methylacryloyl ".Also, as the light irradiated when polymerizeing photopolymerizable compound, visible light can be enumerated The ionizing ray of line and ultraviolet light, X-ray, electron ray, alpha ray, β ray and gamma-rays etc.
As photopolymerizable compound, photopolymerization monomer, optical polymerism oligomer or optical polymerism polymerization can be enumerated Object can carry out these being suitable for using after adjusting.As photopolymerizable compound, preferably photopolymerization monomer and optical polymerism The combination of oligomer or photopolymerization monomer and optical polymerism polymer.
(photopolymerization monomer)
The weight average molecular weight of photopolymerization monomer is less than 1000.As photopolymerization monomer, preferably there are 2 (i.e. 2 officials Can) polyfunctional monomer of above optical polymerism functional group.In this specification, " weight average molecular weight " is dissolved in tetrahydrofuran (THF) rear in equal solvent to be based on the obtained value of polystyrene conversion using conventionally known gel permeation chromatography (GPC) method.
As monomers more than 2 functions, it can be cited for example that trimethylolpropane tris (methyl) acrylate, tripropylene glycol Two (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, pentaerythrite Three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6- oneself two Alcohol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, double three Hydroxymethyl-propane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, tripentaerythritol eight (methyl) propylene Acid esters, tetrapentaerythritol ten (methyl) acrylate, isocyanuric acid three (methyl) acrylate, isocyanuric acid two (methyl) propylene Acid esters, polyester three (methyl) acrylate, polyester two (methyl) acrylate, bis-phenol two (methyl) acrylate, diglycerol four (methyl) acrylate, adamantyl two (methyl) acrylate, isobornyl two (methyl) acrylate, bicyclopentane two (methyl) acrylate, tristane two (methyl) acrylate, double trimethylolpropane four (methyl) acrylate；Or they Substance after modified by po, eo etc..
Among these, from the aspect of obtaining priming coat with high hardness, preferably pentaerythritol triacrylate (PETA), Dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), Dipentaerythritol Pentaacrylate (DPPA) etc..
(optical polymerism oligomer)
The weight average molecular weight of optical polymerism oligomer is 1000 less than 10000.
Multifunctional oligomer as optical polymerism oligomer, more than preferably 2 functions.It, can be with as multifunctional oligomer Enumerate polyester (methyl) acrylate, carbamate (methyl) acrylate, polyester-urethane (methyl) acrylic acid Ester, polyethers (methyl) acrylate, polyalcohol (methyl) acrylate, melamine (methyl) acrylate, isocyanuric acid ester (methyl) acrylate, epoxy (methyl) acrylate etc..
(photopolymerizing prepolymers)
The weight average molecular weight of photopolymerizing prepolymers is 10000 or more, as weight average molecular weight, preferably 10000 or more 80000 hereinafter, more preferably 10000 or more 40000 or less.In the case that weight average molecular weight is more than 80000, due to high viscosity and Cause to be coated with adaptive reduction, the appearance of obtained optical film may deteriorate.As above-mentioned multifunctional polymer, can enumerate Carbamate (methyl) acrylate, isocyanuric acid ester (methyl) acrylate, polyester-urethane (methyl) acrylic acid Ester, epoxy (methyl) acrylate etc..
Polymerization initiator etc. can be used when photopolymerizable compounds are polymerized (crosslinked).Polymerization initiator be by Light irradiation and decompose generate free radicals to cause the polymerization (crosslinking) of photopolymerizable compound or make photopolymerizable compound into The ingredient of row polymerization (crosslinking).
Polymerization initiator is not particularly limited, as long as the substance for causing free radical polymerization can be released after being irradiated by light ?.Polymerization initiator is not particularly limited, well known polymerization initiator can be used, as concrete example it can be cited for example that Acetophenones, benzophenone, michaelis benzoylbenzoic acid ester, α-pentoxime ester (amyloxim ester), thioxanthene ketone class, phenylpropyl alcohol Ketone, benzoin class, benzoin class, acylphosphine oxide class.And it is preferred that mixing photosensitizer carry out using, as its concrete example, It can be cited for example that n-butylamine, triethylamine, poly- normal-butyl phosphine etc..
As above-mentioned polymerization initiator, above-mentioned adhesive resin is the resin system with free-radical polymerised unsaturated group In the case of, preferably acetophenones, benzophenone, thioxanthene ketone class, benzoin, benzoin methylether etc., which are used alone or are mixed, makes With.
Solvent-dry type resin refer to thermoplastic resin etc. only solid component when in order to adjust coating and add Solvent be dried just formed overlay film resin.In the case where adding solvent-dry type resin, when forming priming coat 12,13, The overlay film defect of the coated face of masking liquid can be effectively prevented.Solvent-dry type resin is not particularly limited, can generally be made Use thermoplastic resin.
As thermoplastic resin, it can be cited for example that phenylethylene resin series, (methyl) acrylic resin, vinyl acetate It is resin, vinyl ethers system resin, halogen-containing resin, ester ring type olefin-based resin, polycarbonate-based resin, Polyester tree Rouge, polyamide resin, cellulose derivative, organic silicon-type resin and rubber or elastomer etc..
Thermoplastic resin preferably (can especially dissolve 2 or more polymer amorphism and dissolvable in organic solvent With the general solvent of curability compound).Especially considered from the aspect of transparency and weatherability, optimization styrene system resin, (methyl) acrylic resin, ester ring type olefin-based resin, polyester based resin, cellulose derivative (cellulose esters etc.) etc..
Thermosetting resin is not particularly limited, it can be cited for example that phenol resin, carbamide resin, diallyl phthalate Resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino-alkyd resin, three Poly cyanamid-ureaformaldehyde cocondensation resin, silicone resin, polyorganosiloxane resin etc..
Priming coat 12,13 can be formed: the priming coat containing above-mentioned photopolymerizable compound is coated with composition In the surface of Mght-transmitting base material 11, after dry, the light such as ultraviolet light is irradiated to the priming coat composition of coating, make optical polymerism Compound polymerize (crosslinking), and priming coat 12,13 is consequently formed.
In addition to above-mentioned photopolymerizable compound, priming coat with can according to need in composition addition solvent, polymerization cause Agent.It, can be according to the hardness, inhibition cure shrinkage, control refractive index etc. for improving priming coat also, in priming coat composition Purpose come add conventionally known dispersing agent, surfactant, antistatic agent, silane coupling agent, thickener, anti-coloring agent, Toner (pigment, dyestuff), defoaming agent, levelling agent, fire retardant, ultraviolet absorbing agent, bonding agent, polymerization inhibitor, antioxidant, Surface modifier, lubricant etc..
As the method for painting bottom coating composition, spin coating, infusion process, spray-on process, slip rubbing method, stick can be enumerated Coating method well known to coating, rolling method, gravure, die coating method etc..
As light when solidifying priming coat composition, in the case where using ultraviolet light, can use ultrahigh pressure mercury lamp, The ultraviolet light etc. of the sendings such as high-pressure sodium lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp.Also, the wave as ultraviolet light It is long, the wave band of 190~380nm can be used.As the concrete example of electronic radial source, it can enumerate and examine croft-Wa Erdun (Cockcroft-Walton) type, Van de Graaff type, resonance transformer type, insulating core transformer typ or linear type, The various electron ray accelerators such as Dynamitron type, high-frequency type.
<high refractive index layer>
High refractive index layer 14 preferably has 1.55 or more 1.75 refractive index below.Under the refractive index of high refractive index layer 14 Limit preferably 1.58 or more, the upper limit of the refractive index of high refractive index layer 14 is preferably 1.70 or less.The refraction of high refractive index layer 14 Rate can use method identical with the refractive index of above-mentioned priming coat 12 and be measured.From the side for the fluctuation for further suppressing tone Face considers that the refringence of priming coat 12 and high refractive index layer 14 is preferably 0.05 or more 0.20 or less.
The film thickness of high refractive index layer 14 is preferably 20nm or more 100nm or less.The lower limit of the film thickness of high refractive index layer 14 is more Preferably 30nm or more, the upper limit of the film thickness of high refractive index layer 14 are more preferably 80nm or less, more preferably 70nm or less.
High refractive index layer 14 and low-index layer 15 can be used as making the region equipped with transparency conducting layer 16 and not setting The index matching layer for having the difference of light transmission rate and reflectivity between the region of transparency conducting layer 16 to become smaller plays a role.
High refractive index layer 14 can be made of such as high refractive index particle and adhesive resin.As above-mentioned high refractive index Grain, can enumerate metal oxide microparticle.As metal oxide microparticle, specifically, it can be cited for example that titanium dioxide (TiO2, refractive index: 2.3~2.7), niobium oxide (Nb2O5, refractive index: 2.33), zirconium oxide (ZrO2, refractive index: 2.10), oxidation Antimony (Sb2O5, refractive index: 2.04), tin oxide (SnO2, refractive index: 2.00), tin-doped indium oxide (ITO, refractive index: 1.95~ 2.00), cerium oxide (CeO2, refractive index: 1.95), aluminium-doped zinc oxide (AZO, refractive index: 1.90~2.00), gallium doping oxidation Zinc (GZO, refractive index: 1.90~2.00), zinc antimonates (ZnSb2O6, refractive index: 1.90~2.00), zinc oxide (ZnO, refractive index: 1.90), yttrium oxide (Y2O3, refractive index: 1.87), antimony-doped tin oxide (ATO, refractive index: 1.75~1.85), phosphorus doping oxidation Tin (PTO, refractive index: 1.75~1.85) etc..Among these, from high index of refraction and the preferred zirconium oxide of cost aspect.
Adhesive resin contained by high refractive index layer 14 is not particularly limited, can be used thermoplastic resin, but from It is preferably the polymer such as thermosetting resin or photopolymerizable compound (cross-linking agent) from the aspect of raising surface hardness, wherein more The preferably polymer of photopolymerizable compound.
As thermosetting resin, acrylic resin, carbamate resins, phenol resin, urea melamine can be enumerated Resins such as resin, epoxy resin, unsaturated polyester resin, organic siliconresin etc..It can be used when solidifying thermosetting resin solid Agent.
Photopolymerizable compound is not particularly limited, and photopolymerization monomer, oligomer, polymer can be used.As 1 The photopolymerization monomer of function can enumerate (methyl) ethyl acrylate, (methyl) ethylhexyl acrylate, styrene, methyl Styrene, n-vinyl pyrrolidone etc..Also, as photopolymerization monomers more than 2 functions, it can be cited for example that polyhydroxy first Base propane three (methyl) acrylate, hexylene glycol (methyl) acrylate, tripropylene glycol two (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol Two (methyl) acrylate；Modified compound such as these compound ethane via epoxyethane, polyethylene oxide etc..
Also, these compounds are also possible to by importing halogen atom, sulphur, nitrogen, phosphorus atoms etc. other than aromatic rings, fluorine Compound after refractive index is heightened.In addition, in addition to above-claimed compound, also can be used molecular weight with unsaturated double-bond compared with Low polyester resin, polyether resin, acrylic resin, epoxy resin, carbamate resins, alkyd resin, Luo Suoquanshu Rouge, polybutadiene, polythiol-more olefine resins etc..When photopolymerizable compounds are polymerized (crosslinked), it can be used in primary coat The polymerization initiator illustrated in the item of layer.
High refractive index layer 14 can be formed for example, by method identical with the forming method of priming coat 12,13.Specifically Ground is said, first in the surface of the priming coat 12 coating at least high refractive index layer containing high-refractive index particulate and photopolymerizable compound Use composition.Next, keeping the high refractive index layer composition of coating dry.Thereafter, the high refractive index layer of coating is used Composition irradiates the light such as ultraviolet light, and photopolymerizable compound is polymerized (crosslinking), and thus, it is possible to form high refractive index layer 14.
<low-index layer>
Low-index layer 15 is the layer of the refractive index with the refractive index lower than high refractive index layer 14.Low-index layer 15 The refractive index that there is the refractive index lower than high refractive index layer 14, it may not be necessary to which there is the refractive index lower than priming coat 12 Refractive index.Specifically, the refractive index of low-index layer 15 is preferably 1.35 or more 1.55 or less.The refraction of low-index layer 15 The lower limit of rate is more preferably 1.40 or more, the upper limit of the refractive index of low-index layer 15 more preferably less than 1.52.Low-index layer 15 refractive index can use method identical with the refractive index of above-mentioned priming coat 12 to measure.From the wave for further suppressing tone From the aspect of dynamic, the refringence of high refractive index layer 14 and low-index layer 15 is preferably 0.10 or more 0.30 or less.
The film thickness of low-index layer 15 is preferably 3nm or more 100nm or less.The lower limit of the film thickness of low-index layer 15 is more excellent It is selected as 5nm or more, more preferably 10nm or more.The upper limit of the film thickness of low-index layer 15 be more preferably 80nm or less, further It preferably 60nm or less, is most preferably 45nm or less.
Low-index layer 15 is not particularly limited, as long as the refractive index with the refractive index lower than high refractive index layer 14 is Can, low-index layer 15 can be constituted or be made of low refractive index resin by such as low-refraction particle and adhesive resin.Or Person, low-index layer 15 are also possible to the layer being made of silica, magnesium fluoride etc. to form a film by sputtering.
As low-refraction particle, it can be cited for example that the full particle being made of silica or magnesium fluoride or hollow Grain etc..Among these, preferably hollow silica particle, such hollow silica particle can be for example, by Japanese Unexamined Patent Publications The manufacturing method recorded in the embodiment of 2005-099778 bulletin makes.
As low refractive index particle, it is preferable to use there is the reactive titanium dioxide of reactive functional groups in silica surface Silicon particle.As reactive functional groups, preferably optical polymerism functional group.Such reactive silica particle can pass through benefit Silicon dioxide microparticle is surface-treated with silane coupling agent etc. to make.As micro- to silica using silane coupling agent The method that is handled of surface of grain can be enumerated to silicon dioxide microparticle and be sprayed the dry method of silane coupling agent, by titanium dioxide The silicon particle dispersion damp process etc. that addition silane coupling agent is reacted afterwards in a solvent.
As the adhesive resin for constituting low-index layer 15, the adhesive tree of high refractive index layer 14 can be enumerated and constituted The same adhesive resin of rouge.Wherein, the resin for being imported with fluorine atom, organic poly- silicon oxygen can also be mixed in adhesive resin The low material of the refractive index such as alkane.
As low refractive index resin, it is low that the refractive index such as the resin for being imported with fluorine atom, organopolysiloxane can be enumerated Resin.
Low-index layer 15 can be formed for example, by method identical with the forming method of priming coat 12.Specifically, First in the surface of the high refractive index layer 14 coating at least low-index layer containing low refractive index particle and photopolymerizable compound Use composition.Next, keeping the composition for low refractive index layer of coating dry.Thereafter, the low-index layer of coating is used Composition irradiates the light such as ultraviolet light, and photopolymerizable compound is polymerized (crosslinking), and thus, it is possible to form low-index layer 15.
<transparency conducting layer>
Transparency conducting layer 16 is set on low-index layer 15 and patterns.The refractive index of transparency conducting layer 16 is preferably 1.85 Above 2.30 or less.The lower limit of the refractive index of transparency conducting layer 16 is preferably 1.90 or more, the refractive index of transparency conducting layer 16 The upper limit is preferably 2.20 or less.The refractive index of transparency conducting layer 16 can use side identical with the refractive index of above-mentioned priming coat 12 Method measurement.
The film thickness of transparency conducting layer 16 is preferably 15nm or more 50nm or less.The lower limit of the film thickness of transparency conducting layer 16 is more excellent It is selected as 20nm or more, the upper limit of the film thickness of transparency conducting layer 16 is more preferably 45nm or less.
Transparency conducting layer 16 be containing for example inorganic system's transparency conducting layer material, organic system transparency conducting layer material, Or the layer of the mixing material of inorganic system's transparency conducting layer material and organic system transparency conducting layer material.As it is inorganic be transparent Conductive layer material can enumerate tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), zinc oxide, indium oxide (In2O3), aluminium-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), tin oxide, zinc oxide-Sn system, indium oxide-oxygen Change metal oxides, the carbon nanotubes such as tin system, zinc oxide-indium oxide-magnesia system etc..Among these, from transparency conducting layer Transparent and low-resistance aspect is set out, as the inorganic preferred tin-doped indium oxide of system's transparency conducting layer material (ITO).As Organic system transparency conducting layer material can enumerate electric conductive polymer etc..
The forming method of transparency conducting layer 16 is not particularly limited, sputtering method, vacuum vapour deposition, ion can be used Plating method, CVD method, rubbing method, print process etc..Patterned method is carried out as to transparency conducting layer, it can be cited for example that photograph Lithography.
The patterning of transparency conducting layer 16 can be as shown in Figure 2 for shape.Transparency conducting layer 16 shown in Fig. 2 The portion of terminal (not shown) for having sensor portion 16A, being linked in sensor portion.Sensor portion 16A is set to rectangular-shaped active region (ア Network テ ィ Block エ リ ア) in, which is the region for being able to detect that contact position, and portion of terminal is set to inactive area Interior, the inactive area is adjacent with active region, surrounds active region from surrounding.
Sensor portion 16A is configured in a predetermined pattern.Specifically, sensor portion 16A is configured to along conductive film 10 Low-index layer 15 film surface arranged in parallel in a direction line-shaped conductive body.
Each line-shaped conductive body of sensor portion 16A is formed in the direction intersected with its orientation (one direction) On with threadiness extend.In Fig. 2, sensor portion 16A is (described another along the direction orthogonal with its orientation (one direction) One direction) linearly to extend.
Sensor portion 16A is with the straight line portion 16B linearly extended and by the bulge 16C of straight line portion 16B bulging. In Fig. 2, straight line portion 16B is along the direction that the orientation with sensor portion 16A intersects linearly to extend.Bulge 16C is Along conductive film 10 low-index layer 15 film surface by straight line portion 16B bulging part.Therefore, each sensor portion 16B Width can become larger in the part equipped with bulge 16C.In present embodiment, bulge 16C, which has to overlook, is substantially square shape Outer profile.It should be noted that bulge 16C is not limited to overlook the shape that is substantially square, be also possible to diamond shaped or Striated.
In the prior art, the refractive index and film thickness of low-index layer of conductive film etc. is mainly due to reduce by translucency The reflectivity and lamination for the intermediate base material film that substrate, high refractive index layer and low-index layer are constituted are in transparent in intermediate base material film The viewpoint of the difference (reflection differences) of the reflectivity of conductive layer determines, tone when as intermediate base material film watch at different angles Fluctuation and be not affected by any concern.On the other hand, compared with above-mentioned reflection differences, human eye is easier to experience the change of tone Change, also, increases high refractive index layer and low-index layer to reduce the reflection differences of intermediate base material film and transparency conducting layer Refringence when, with tone fluctuation bigger tendency.The present inventor is by repeatedly further investigation discovery, to electric conductivity The a* value and b* value of film are able to suppress the fluctuation of tone when being adjusted.Specifically, being found through experiments that, by transparency conducting layer Lateral transparency conducting layer irradiation light, and the normal to a surface direction of conductive film is set as 0 °, in 5 ° or more 75 ° or less of range Every 5 degree of ground transformation incident angle is irradiated, and finds out L*a*b* coloration system by the respective reflected light towards mirror-reflection direction When the a* value and b* value of system, the fluctuation of a* value is within 3.5, and when the fluctuation of b* value is within 7.0, even if observer is with various In the case that conductive film is watched in direction, it will not recognize that fluctuation occurs in tone.According to the present embodiment, by electrically conducting transparent Layer 16 the surface side 16A to 16 irradiation light of transparency conducting layer, and set conductive film 10 surface 10A normal direction as 0 °, Every 5 degree of ground transformation incident angle is irradiated in 5 ° or more 75 ° or less of range, by respective towards the anti-of mirror-reflection direction When penetrating light and finding out the a* value and b* value of L*a*b* colorimeter system, the fluctuation of a* value is within 3.5, and the fluctuation of b* value be 7.0 with It is interior, therefore, it is able to suppress the fluctuation of the tone in the case where watching conductive film 10 with various angles.
Also, the present inventor is by further investigation discovery repeatedly, by high refractive index layer, low-index layer and transparent Refractive index of conductive layer etc. carries out being suitable for adjustment, can be within 3.5 and to incite somebody to action the undulated control of the a* value of above-mentioned conductive film The undulated control of b* value is within 7.0.Specifically, the inventors discovered that, such as have by being formed on Mght-transmitting base material The high refractive index layer of the refractive index below of 20nm or more 100nm film thickness below and 1.55 or more 1.75 has 3nm or more The low-index layer of the refractive index below of 100nm film thickness below and 1.35 or more 1.55 and have 15nm or more 50nm with Under 2.30 refractive index below of film thickness and 1.85 or more transparency conducting layer, can be by the fluctuation of the a* value of above-mentioned conductive film It is within 7.0 that control, which is within 3.5 and by the undulated control of b* value,.Having the high refraction with above-mentioned refractive index and film thickness In the conductive film of rate layer, low-index layer and transparency conducting layer, although the reflection differences of intermediate base material film and transparency conducting layer In permissible range, but compared with existing intermediate base material film, it can become larger with the reflection differences of transparency conducting layer, it is therefore, such as existing Technology is the technology that will never be used like that from the aspect of the reflection differences for reducing intermediate base material film and transparency conducting layer Scheme.Accordingly, it can be said that compare the technical level of existing intermediate base material film, by by high refractive index layer, low-index layer and What the refractive index and film thickness of transparency conducting layer was played in above range in above range and by a* value and b* value Said effect be above can prediction range significant effect.
<<contact panel sensor>>
Conductive film 10 can be installed in, for example, a touch panel sensor carry out using.
The conductive film 10 of contact panel sensor 20 shown in Fig. 4 and structure made of 21 lamination of conductive film.It should Figure is the II-II line sectional view of Fig. 5.
Conductive film 10 has the patterned transparency conducting layer 16 supported by low-index layer 15.Conductive film 21 Has the patterned transparency conducting layer 22 supported by low-index layer 15.It is deposited between conductive film 10 and conductive film 21 In transparent adhesion coating 23, conductive film 10 is sticked together with conductive film 21 by transparent adhesion coating 23.On conductive film 10 Equipped with transparent adhesion coating 24.
Observer side of the configuration of transparency conducting layer 16 in the low-index layer 15 for constituting conductive film 10, transparency conducting layer 22 The observer side configured in the low-index layer 15 for constituting conductive film 21.That is, the configuration of transparency conducting layer 22 is constituting electric conductivity Between the low-index layer 15 of film 21 and the priming coat 13 for constituting conductive film 10.
As shown in figure 5, the terminal that transparency conducting layer 16,22 has sensor portion 16A, 22A respectively, is linked in sensor portion Portion (not shown).Sensor portion 16A, 22A is set in rectangular-shaped active region, which is to be able to detect that connect The region of position is touched, portion of terminal is set in inactive area, and the inactive area is adjacent with active region, surrounds active region from surrounding.It needs It is noted that transparency conducting layer 16, sensor portion 16A, straight line portion 16B, bulge 16C are same as shown in Figure 2.
Sensor portion 22A different from the scheduled pattern of sensor portion 16A to configure.Specifically, sensor portion 16A with Along conductive film 10 low-index layer 15 film surface in a direction the line-shaped conductive body of arranged in parallel form constitute, pass Sensor portion 22A with one direction to intersect and along the film surface of the low-index layer of conductive film 21 15 by another direction The form of the line-shaped conductive body of arranged in parallel is constituted.In present embodiment, touch panel viewed from above is passed as shown in Figure 5 When sensor 20, a direction of the orientation as sensor portion 16A is another with the orientation as sensor portion 22A A direction is orthogonal.
Each line-shaped conductive body of sensor portion 22A is formed in the side intersected with its orientation (another described direction) Extended upwards with threadiness.In Fig. 5, sensor portion 22A is along the direction (institute orthogonal with its orientation (another described direction) State a direction) linearly to extend.
Sensor portion 22A is constituted in the same manner as sensor portion 16A.That is, sensor portion 22A is with straight with what is linearly extended Line portion 22B and bulge 22C by straight line portion 22B bulging.In Fig. 5, straight line portion 22B is along the arrangement side with sensor portion 22A To the direction of intersection linearly to extend.Bulge 22C is the film surface along the low-index layer 15 of conductive film 21 by straight line The part of portion's 22B bulging.Therefore, the width of each sensor portion 22B can become larger in the part equipped with bulge 22C.This embodiment party In formula, bulge 22C has the outer profile overlooked and be substantially square shape.It should be noted that bulge 22C is not limited to overlook It is substantially square the shape of shape, is also possible to diamond shaped or striated.
It should be noted that as shown in figure 5, in the case where from the normal direction of contact panel sensor 20 (that is, In top view), sensor portion 16A intersects with many sensor portion 22A.Also, as shown in figure 5, the bulge of sensor portion 16A 16B is configured between the crosspoint of two adjacent sensor portion 22A on sensor portion 16A.Similarly, from touch panel In the case where the normal direction observation of sensor 20, sensor portion 22A intersects with many sensor portion 16A.Also, sensor portion The bulge 22C of 22A is also configured between the crosspoint of two adjacent sensor portion 16A on sensor portion 22A.This Outside, in present embodiment, the bulge 22C of the bulge 16C and sensor portion 22A of sensor portion 16A is according to from touch panel The mode that will not be overlapped in the case where the normal direction observation of sensor 20 configures.That is, from the normal of contact panel sensor 20 In the case that direction is observed, sensor portion 16A only intersects at straight line portion 16B, 22B with sensor portion 22A.
<transparent adhesion coating>
As transparent adhesion coating 23,24, well known pressure-sensitive adhesive layer, adhesive sheet can be enumerated.
<<other contact panel sensors>>
Conductive film 10 can also be installed on the contact panel sensor of other modes.Touch panel sensing shown in fig. 6 Device 30 have conductive film 10, glass plate 31, the transparency conducting layer 32 being formed on a face of glass plate 31, by conductive film 10 and the transparent adhesion coating 33 that is fixed up of the glass plate 31 with transparency conducting layer 32.Transparency conducting layer 32 and transparency conducting layer 22 is identical, and and the description is omitted.
[the 2nd embodiment]
The conductive film and contact panel sensor of the 2nd embodiment of the invention are illustrated referring to the drawings. Fig. 7 is the schematic constitution diagram of the conductive film of present embodiment.It should be noted that being imparted and the 1st in present embodiment The component of the component the same symbol illustrated in embodiment is meant to be identical with the component illustrated in the 1st embodiment Component, also, for the 1st duplicate content of embodiment, the description thereof will be omitted as long as not being specially recorded.
Conductive film 40 shown in Fig. 7 has: Mght-transmitting base material 11；Lamination is in the priming coat on the two sides of Mght-transmitting base material 11 12,13；The high refractive index layer 14,41 being formed on priming coat 12,13；The low-refraction being formed on high refractive index layer 14,41 Layer 15,42；The transparency conducting layer 16,43 being formed on low-index layer 15,42.That is, conductive film 40 is in conductive film 10 High refractive index layer 41, low-index layer 42, transparency conducting layer 43 are laminated on priming coat 13.Conductive film 40 has priming coat 12,13, however, you can also not have priming coat 12 and/or priming coat 13.The surface 16A of transparency conducting layer 16 forms conductive film 40 Surface 40A.High refractive index layer 41 is identical as high refractive index layer 14, and low-index layer 42 is identical as low-index layer 15, and Transparency conducting layer 43 is identical as transparency conducting layer 22, and and the description is omitted.
In conductive film 40, from the surface side 16A of transparency conducting layer 16 to 16 irradiation light of transparency conducting layer (visible light), and If the normal direction of the surface 40A of conductive film 40 is 0 °, every 5 degree incidence angle is converted in 5 ° or more 75 ° or less of range Degree is irradiated, when finding out the a* value and b* value of L*a*b* colorimeter system by the respective reflected light towards mirror-reflection direction, The fluctuation of a* value be 3.5 within, and the fluctuation of b* value be 7.0 within.The fluctuation of a* value is preferably within 1.5, and b* value Within fluctuation preferably 5.5.
According to the present embodiment, from the surface side 16A of transparency conducting layer 16 to 16 irradiation light of transparency conducting layer, and conduction is set Property film 40 surface 40A normal direction be 0 °, every 5 degree converted in 5 ° or more 75 ° or less of range incident angle carry out Irradiation, when finding out the a* value and b* value of L*a*b* colorimeter system by the respective reflected light towards mirror-reflection direction, a* value Fluctuation is within 3.5, and the fluctuation of b* value is within 7.0, therefore, for identical as the reasons why explanation in the 1st embodiment The reasons why, it is able to suppress the fluctuation of the tone in the case where watching conductive film 40 with various angles.
" contact panel sensor "
Conductive film 40 can be installed in, for example, a touch panel sensor carry out using.Fig. 8 is to be equipped with this embodiment party The schematic constitution diagram of the contact panel sensor of the conductive film of formula.
Contact panel sensor 50 shown in Fig. 8 has conductive film 40 and set on the transparent viscous of the two sides of conductive film 40 Layer 51,52.
Transparency conducting layer 16,43 is formed in the two sides of conductive film 40, therefore the patterning of transparency conducting layer 16,43 can be with It is primary to carry out.
[the 3rd embodiment]
The conductive film and contact panel sensor of the 3rd embodiment of the invention are illustrated referring to the drawings. Fig. 9 is the schematic constitution diagram of the conductive film of present embodiment, and Figure 10 is showing for other conductive films of present embodiment Meaning property constitutes figure.
<<conductive film>>
Conductive film 60 shown in Fig. 9 has Mght-transmitting base material 11, lamination in the height on a face of Mght-transmitting base material 11 Index layer 61, low-index layer 62, transparency conducting layer 63 are also equipped with lamination in the bottom on another face of Mght-transmitting base material 11 Coating 13.In conductive film 60, priming coat is not provided between Mght-transmitting base material 11 and high refractive index layer 61.Conductive film 60 has Priming coat 13 is had, however, you can also not have priming coat 13.The surface 63A of transparency conducting layer 63 forms the surface of conductive film 60 60A。
Conductive film 70 shown in Fig. 10 has Mght-transmitting base material 11, lamination in the height on a face of Mght-transmitting base material 11 Index layer 61, low-index layer 62, transparency conducting layer 63 are also equipped with lamination in the height on another face of Mght-transmitting base material 11 Index layer 71, low-index layer 72, transparency conducting layer 73.In conductive film 70, Mght-transmitting base material 11 and high refractive index layer 61, Priming coat is not provided between 71.The surface 63A of transparency conducting layer 63 forms the surface 70A of conductive film 70.
Other than film thickness, high refractive index layer 61,71 and 14 phase of high refractive index layer illustrated in the first embodiment described above Together.The film thickness of high refractive index layer 61,71 is 0.5 μm or more 10 μm or less.By 0.5 μ of film thickness for making high refractive index layer 61,71 M or more can also be obtained and electric conductivity even if priming coat is not arranged between Mght-transmitting base material 11 and high refractive index layer 61,71 Film 10,40 same hardness.Also, passed through by making 10 μm of film thickness of high refractive index layer 61,71 hereinafter, being able to suppress Roll-to-roll produces the crackle of the high refractive index layer occurred when conductive film.
The lower limit of the film thickness of high refractive index layer 61,71 is more preferably 1.0 μm or more, the film thickness of high refractive index layer 61,71 The upper limit is more preferably 5.0 μm or less.
In conductive film 60, from the surface side 63A of transparency conducting layer 63 to 63 irradiation light of transparency conducting layer (visible light), and If the normal direction of the surface 60A of conductive film 60 is 0 °, every 5 degree incidence angle is converted in 5 ° or more 75 ° or less of range Degree is irradiated, when finding out the a* value and b* value of L*a*b* colorimeter system by the respective reflected light towards mirror-reflection direction, The fluctuation of a* value be 3.5 within, and the fluctuation of b* value be 7.0 within.
In conductive film 70, from the surface side 63A of transparency conducting layer 63 to 63 irradiation light of transparency conducting layer (visible light), and If the normal direction of the surface 70A of conductive film 70 is 0 °, every 5 degree incidence angle is converted in 5 ° or more 75 ° or less of range Degree is irradiated, when finding out the a* value and b* value of L*a*b* colorimeter system by the respective reflected light towards mirror-reflection direction, The fluctuation of a* value be 3.5 within, and the fluctuation of b* value be 7.0 within.
The fluctuation of a* value is preferably within 1.5 in conductive film 60,70, and the fluctuation of b* value is preferably within 5.5.
According to the present embodiment, from the surface side 63A of transparency conducting layer 63 to 63 irradiation light of transparency conducting layer, and conduction is set Property film 60,70 surface 60A, 70A normal direction be 0 °, every 5 degree convert incidence angle in 5 ° or more 75 ° or less of range Degree is irradiated, when finding out the a* value and b* value of L*a*b* colorimeter system by the respective reflected light towards mirror-reflection direction, The fluctuation of a* value is within 3.5, and the fluctuation of b* value is within 7.0, therefore, for the reason that illustrated in the 1st embodiment By identical reason, be able to suppress from various angles watch conductive film 60,70 in the case where tone fluctuation.
<<contact panel sensor>>
Conductive film 60,70 can be installed on identical with Fig. 4, Fig. 6 and contact panel sensor structure shown in Fig. 8 Contact panel sensor.
(the 2nd mode of the invention)
[the 2nd embodiment]
The 2nd embodiment of the invention is described in detail below.
The present inventor is successively laminated with priming coat, high refractive index layer and low-refraction on a face of Mght-transmitting base material It layer and is had made intensive studies for the hard coat film of contact panel sensor, as a result, it has been found that, by above-mentioned low-index layer Scheduled concaveconvex shape is formed on surface, and it is excellent but also conductive layer is being formed in above-mentioned low folding can to obtain not only lubricity The hard coat film of the low resistance value of the conductive layer is able to achieve when penetrating on rate layer, so as to complete the present invention.
Hard coat film of the invention is successively laminated with priming coat (also referred to as hard conating), high refractive index layer on Mght-transmitting base material And low-index layer.In such hard coat film of the invention, above-mentioned low-index layer has concaveconvex shape on surface, uses scanning Type white Gan Wataru microscope is flat in 10 points for measuring visual field 0.12mm (0.12 millimeter of square, the hereinafter also referred to big visual field) measurement Equal roughness and the value of arithmetic average roughness, which are all larger than, is measuring 5 μm of visual field (below using scanning type probe microscope Referred to as micro- visual field) measurement 10 mean roughness and arithmetic average roughness value.It should be noted that hard painting of the invention In film, as above-mentioned sweep type white interference microscope, specifically, the manufacture of Zygo Corporation society can be enumerated " Zygo NewView 6300 ", " Zygo New View 7300 " etc., as above-mentioned scanning type probe microscope, specifically, The SPM-9600 etc. of Shimadzu Seisakusho Ltd.'s manufacture can be enumerated.
The above-mentioned value with 10 mean roughness of big visual field measurement and arithmetic average roughness is to indicate to influence lubrication Property above-mentioned low-refraction layer surface formed biggish concaveconvex shape state parameter, it is above-mentioned with micro- visual field measurement ten Point mean roughness and arithmetic average roughness are to indicate to contribute to form in the low-resistance value of the conductive layer on low-index layer The parameter of the state for the smaller concaveconvex shape formed in above-mentioned low-refraction layer surface changed, since these parameters have above-mentioned pass System, therefore the lubricity of hard coat film of the invention is excellent, can be realized the raising for being formed by the low resistance value of conductive layer.
In hard coat film of the invention, 10 mean roughness in the big visual field of preferably above-mentioned low-refraction layer surface are 50 ~500nm, arithmetic average roughness are 0.5~10.0nm.When 10 mean roughness in the above-mentioned big visual field are less than 50nm, profit Slip is insufficient, adhesion resistance possible deviation, when more than 500nm, it is seen that gonorrhoea sense (albefaction), the transparency may be decreased.Also, When arithmetic average roughness in the above-mentioned big visual field is less than 0.5nm, lubricity is insufficient, and adhesion resistance possible deviation is more than When 10.0nm, it is seen that gonorrhoea sense (albefaction), the transparency may be decreased.10 mean roughness in the above-mentioned big visual field are preferred Lower limit is 150nm, the preferred upper limit is 400nm, and the preferred lower limit of arithmetic average roughness in the above-mentioned big visual field is 1.0nm, the preferred upper limit are 6.0nm.
It should be noted that 10 mean roughness in the above-mentioned big visual field are based on regulation in JIS B0601 (1994) Rz handled and calculated value, the arithmetic average roughness in the above-mentioned big visual field is based in JIS B0601 (1994) Defined Ra is handled and calculated value, be both using sweep type white Gan Wataru microscope measurement the visual field 0.05~ The value that 0.3mm is determined.Also, as above-mentioned sweep type white interference microscope, specifically, Zygo can be enumerated " Zygo New View 6300 ", " the Zygo New View 7300 " of Corporation society manufacture.On it should be noted that State arithmetic average roughness in the big visual field and 10 mean roughness based on Ra specified in JISB0601 (2001) and Also can similarly it be worth when RzJIS is handled and calculated.
Also, it is preferred that 10 mean roughness in micro- visual field of above-mentioned low-refraction layer surface are 50nm hereinafter, arithmetic Mean roughness is 3.0nm or less.When 10 mean roughness in above-mentioned micro- visual field are more than 50nm, due to low-index layer Concave-convex surface and the disadvantages of crackle when being easy to appear conductive layer film forming, film thickness it is uneven, it is difficult to realize and formed on low-index layer Conductive layer low resistance, and the fluctuation of the resistance value of conductive layer may become larger, and above-mentioned arithmetic average roughness is more than When 3.0nm, due to low-index layer concave-convex surface and the disadvantages of crackle when being easy to appear conductive layer film forming, film thickness it is uneven, It is difficult to realize the low resistance of conductive layer formed on low-index layer, and the fluctuation of the resistance value of conductive layer may become larger. 10 preferred upper limits of mean roughness in above-mentioned micro- visual field are 1.0nm, the arithmetic average roughness in above-mentioned micro- visual field The preferred upper limit is 2.5nm.
It should be noted that 10 mean roughness in above-mentioned micro- visual field are based on regulation in JIS B0601 (2001) RzJIS handled and calculated value, the arithmetic average roughness in above-mentioned micro- visual field is based on JIS B0601 (2001) Specified in Ra handled and calculated value, be both using scanning type probe microscope measurement 1~10 μm of the visual field The value that is determined.Also, as above-mentioned scanning type probe microscope, specifically, Shimadzu Seisakusho Ltd.'s manufacture can be enumerated SPM-9600 etc..It should be noted that the arithmetic average roughness and 10 mean roughness in above-mentioned micro- visual field are being based on JIS Ra and Rz specified in B0601 (1994) also can be similarly worth when being handled and being calculated.
It should be noted that in the either case in the big visual field and micro- visual field, 10 points are put down when illustrating in the following description Equal roughness meter is shown as " Rz ", arithmetic average roughness is expressed as " Ra ".
Above-mentioned Mght-transmitting base material is not particularly limited, it can be cited for example that polyester based resin, acetic acid esters system resin, polyethers Sulfone system resin, polycarbonate-based resin, polyamide resin, polyimides system resins, polyolefin-based resins, (methyl) acrylic acid It is resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate It is resin, polyphenylene sulfide system resin etc..It is wherein suitable for using polyester based resin, polycarbonate-based resin, polyolefin-based resins.
The thickness of above-mentioned Mght-transmitting base material is preferably 15~200 μm.It is easy to produce fold when less than 15 μm, is manufacturing this hair When bright hard coat film, the operation for being continuously formed priming coat etc. on Mght-transmitting base material sometimes can be become difficult.On the other hand, surpass When crossing 200 μm, when manufacturing hard coat film of the invention, web-like, Huo Zhe may be made in Mght-transmitting base material with can not be successfully The filming of contact panel sensor, lightweight and cost effective aspect are unfavorable.The thickness of above-mentioned Mght-transmitting base material is preferred Lower limit is 50 μm, the preferred upper limit is 125 μm.
Above-mentioned Mght-transmitting base material can implement sputtering, corona discharge, ultraviolet light irradiation, electron ray photograph on surface in advance Etching processes or the primary coat processing such as penetrate, be melted into, aoxidizing.By implementing these processing in advance, can be improved its be formed in it is above-mentioned The adaptation of priming coat on Mght-transmitting base material.Also, it is formed before priming coat or conductive layer, can according to need and pass through solvent Cleaning or ultrasonic cleaning etc. are dusted Mght-transmitting base material surface, clean.
In hard coat film of the invention, above-mentioned priming coat, high refractive index layer and low-index layer preferably comprise particle.On if State that the particle that the particle that priming coat contains is particle a, above-mentioned high refractive index layer contains is particle b, above-mentioned low-index layer contains Particle when being particle c, under the preferably above-mentioned particle a of hard coat film of the invention, particle b and the respective average grain diameter of particle c meet The relationship of formula (1).
The average grain diameter of particle a > particle b average grain diameter > particle c average grain diameter (1)
By meeting the relationship of above-mentioned formula (1), hard coat film of the invention can become high refractive index layer and low-index layer Adaptation is extremely excellent, film-strength also excellent hard coat film simultaneously.
In above-mentioned high refractive index layer and low-index layer containing the suitable particle b for becoming respective desired refractive index and Particle c, in such high refractive index layer and low-index layer, when observing the section of each layer, due to the average grain of above-mentioned particle b Diameter is greater than above-mentioned particle c, therefore the sectional area of the particle b in the appearance of the section of above-mentioned high refractive index layer is less than in above-mentioned low refraction The sectional area for the particle c that the section of rate layer occurs.About this point it may be speculated that with more density in above-mentioned high refractive index layer Mode includes particle b, as a result, at the interface of above-mentioned high refractive index layer and above-mentioned low-index layer, above-mentioned high refractive index layer institute The part that the aftermentioned binder resin b contained is contacted with above-mentioned low-index layer becomes more, above-mentioned high refractive index layer and low refraction The adaptation of rate layer becomes excellent.
Also, in the above-mentioned low-index layer containing particle c, by above-mentioned formula (1) it is found that particle c is average grain diameter minimum Particle, due to above-mentioned micro- on the surface (surface with the face opposite side of high refractive index layer side) of above-mentioned low-index layer The Rz and Ra of the concaveconvex shape of grain c become smaller, and flatness is extremely excellent.When the low-index layer is smooth, aftermentioned conductive layer is formed In the case where, the film forming of the conductive layer is good, and the disadvantages of being less prone to crackle and film thickness are uneven, is easy the same of low resistance When, the fluctuation of resistance value also inhibits smaller.
The Rz and Ra measured in above-mentioned micro- visual field indicates the recessed of the surface of the above-mentioned low-index layer due to above-mentioned particle c The parameter of convex form, in the case where the surface of the low-index layer forms conductive layer, the shape preferably on the surface of the conductive layer At the concaveconvex shape for the concaveconvex shape for having the surface for substantially maintaining above-mentioned low-index layer.The surface of above-mentioned low-index layer Concaveconvex shape on (surface of the side opposite with the face of high refractive index layer side) due to above-mentioned particle c formation is in above-mentioned micro- view In the case that the Rz and Ra of open country measurement meet above-mentioned relationship, flatness becomes extremely excellent, and the surface of above-mentioned conductive layer is risen Because the Rz and Ra of the concaveconvex shape in above-mentioned particle c also become smaller, flatness becomes extremely excellent.
It should be noted that above-mentioned " substantially maintaining the concaveconvex shape on the surface of low-index layer " is it is meant that in expression It states the parameter of the concaveconvex shape on the surface of low-index layer and indicates the parameter of the concaveconvex shape on the surface of above-mentioned conductive layer substantially For identical value.Therefore, the surface of above-mentioned low-index layer be formed with the concaveconvex shape on the surface of above-mentioned conductive layer, the transparency and The optical properties such as preventing property of interference fringe are the concaveconvex shape of equal extent.
In hard coat film of the invention, the average grain diameter of above-mentioned particle a, b and c refer to following calculated several average values: root According to section electron microscope (preferably TEM, STEM etc. of the thickness direction of above-mentioned priming coat, high refractive index layer and low-index layer Transmission-type and multiplying power are 50,000 times or more) image, using the image processing software built in the electron microscope, for above-mentioned micro- The major diameter and minor axis of grain a, b and c respectively measure 10, calculate several mean values.It should be noted that the measurement of above-mentioned average grain diameter is not The case where particle only for measure object is individual particle, it is solidifying with this in the case which is agglutinating particle made of agglutination Collection particle is similarly measured as 1.
In hard coat film of the invention, the above-mentioned preferred lamination of the priming coat containing particle a is on above-mentioned Mght-transmitting base material.And And the above-mentioned preferred average grain diameter of particle a is greater than above-mentioned particle b and c.The priming coat of such particle a big containing average grain diameter Lamination is on above-mentioned Mght-transmitting base material, and hard coat film of the invention can be formed on the surface of aftermentioned low-index layer as a result, Due to the concaveconvex shape a of above-mentioned particle a.The concaveconvex shape a on the surface of such low-index layer preferably satisfies above-mentioned big Rz and Ra in the visual field.Also, since above-mentioned concaveconvex shape a is formed in the surface of above-mentioned low-index layer, this can be made The lubricity of the hard coat film of invention becomes excellent.Since the lubricity of hard coat film of the invention is excellent, for of the invention The productivity when forming of hard coat film improve etc. viewpoints batch roller is made when, can suitably prevent overlapping Film the phenomenon that being adhering to each other (so-called adhesion).
Also, in hard coat film of the invention, even if existing on the surface on above-mentioned priming coat than aftermentioned concaveconvex shape a Finer concaveconvex shape (radio-frequency component), the radio-frequency component of the concaveconvex shape is also due to above-mentioned high refractive index layer and low folding The rate layer of penetrating is formed on the priming coat and is buried.Therefore, it not will form on the surface of above-mentioned low-index layer due to above-mentioned The concaveconvex shape of the radio-frequency component on the surface of priming coat.It therefore, can be abundant as described above, in the case where foring conductive layer Acquisition film forming is good, is easy to low resistance while inhibiting the fluctuation of resistance value to obtain smaller such effect.
It should be noted that above-mentioned particle a can be included in above-mentioned priming coat with the state of individual particle, it can also be with solidifying The state for collecting particle is included in above-mentioned priming coat, and under any state, average grain diameter is all satisfied above-mentioned relation.
Above-mentioned particle a is not particularly limited, it can be cited for example that organic fine particles and/or inorganic particles.To above-mentioned inorganic Particle is not particularly limited, and is suitable for using such as inorganic oxide particle, as the inorganic oxide particles, it can be cited for example that Silicon dioxide microparticle, alumina particulate, zirconia particles, titanium dioxide fine particles, tin oxide particles, ATO particle, zinc oxide are micro- Grain, colloidal silica particulate etc..As above-mentioned inorganic particles, more from the hydrothermal stability aspect of above-mentioned priming coat It is preferred that silicon dioxide microparticle, the concaveconvex shape on the surface due to being capable of forming aftermentioned low-index layer suitably assign lubrication Property, therefore more preferably spherical silicon dioxide particle or colloidal silica particulate.It should be noted that as above-mentioned " spherical " Meaning it can be cited for example that just spherical, oval spherical etc., do not include so-called amorphous.
Above-mentioned organic fine particles are not particularly limited, it can be cited for example that high density polyethylene (HDPE), molecular weight be 300000 with On ultra high molecular polyethylene, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate third The particle of ester resin, acrylic resin and their copolymers etc..
The preferred average grain diameter of particle a that above-mentioned priming coat contains is 0.1~3.0 μm.It, possibly can not be when less than 0.1 μm The surface of aftermentioned low-index layer forms desired concaveconvex shape and assigns lubricity, when more than 3.0 μm, particle a relative to The film thickness of priming coat becomes excessive, gonorrhoea sense occurs, the transparency may be damaged.The average grain diameter of above-mentioned particle a it is more preferable Lower limit be 0.5 μm, the preferred upper limit is 2.0 μm.It should be noted that the average grain diameter of above-mentioned particle a is not only for this The case where particle a is individual particle, it is also preferred that being in above range in the case where being contained in priming coat in the form of agglutination body.
Above-mentioned priming coat preferably comprises binder resin a and particle a, relative to the above-mentioned binder resin a of 100 mass parts, Preferably comprise 0.05~10.0 mass parts particle a.If possibly can not be in aftermentioned low-index layer less than 0.05 mass parts Surface forms desired concaveconvex shape and assigns lubricity, if more than 10.0 mass parts, possibly can not in aftermentioned low refraction The surface of rate layer forms desired concaveconvex shape, and the transparency of above-mentioned priming coat may reduce.Above-mentioned particle a's contains The preferred lower limit of amount is 0.1 mass parts, the preferred upper limit is 5.0 mass parts.
The resin of above-mentioned binder resin a preferably clear, preferably for example as solid by ultraviolet light or electron ray The ionizing radiation curable resin of the resin of change by ultraviolet light or electron ray irradiation and the resin after solidifying.It needs to illustrate , in this specification, unless otherwise specified, " resin " is the concept for including monomer, oligomer, polymer etc..
As above-mentioned ionizing radiation curable resin, it can be cited for example that the chemical combination of the functional group with acrylic ester etc. Object etc. has the compound of 1 or 2 or more unsaturated bond.As the compound with 1 unsaturated bond, it can be cited for example that (methyl) ethyl acrylate, (methyl) ethylhexyl acrylate, styrene, methyl styrene, n-vinyl pyrrolidone etc..Make For the compound with 2 or more unsaturated bonds, it can be cited for example that trimethylolpropane tris (methyl) acrylate, 3 the third two Alcohol two (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, Ji Wusi Alcohol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6- oneself It is glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, double Trimethylolpropane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, tripentaerythritol eight (methyl) third Olefin(e) acid ester, tetrapentaerythritol ten (methyl) acrylate, isocyanuric acid three (methyl) acrylate, isocyanuric acid two (methyl) third Olefin(e) acid ester, polyester three (methyl) acrylate, polyester two (methyl) acrylate, bis-phenol two (methyl) acrylate, diglycerol Four (methyl) acrylate, adamantyl two (methyl) acrylate, isobornyl two (methyl) acrylate, bicyclopentane two More officials such as (methyl) acrylate, tristane two (methyl) acrylate, double trimethylolpropane four (methyl) acrylate Energy compound etc..Wherein be suitable for using pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA) and Pentaerythritol tetraacrylate (PETTA).It should be noted that " (methyl) acrylate " refers to methyl in this specification Acrylate and acrylate.Also, in the present invention, above compound can be used as above-mentioned ionizing radiation curable resin Substance after modified by po, eo etc..
Other than above compound, can also use the relatively low polyester resin of molecular weight with unsaturated double-bond, Polyether resin, acrylic resin, epoxy resin, carbamate resins, alkyd resin, spiral shell acetal resin, polybutadiene tree Rouge, polythiol-more olefine resins etc. are used as above-mentioned ionizing radiation curable resin.
Above-mentioned ionizing radiation curable resin can also with solvent-dry type resin (thermoplastic resin etc., will only be coated with when The solvent seasoning added for adjusting solid component just becomes the resin of overlay film) share after use.By sharing solvent seasoning Type resin can be effectively prevented the overlay film defect of the coated face of masking liquid when forming priming coat.
The solvent-dry type resin used after capable of sharing with above-mentioned ionizing radiation curable resin is not particularly limited, Thermoplastic resin generally can be used.Such thermoplastic resin is not particularly limited, it can be cited for example that polystyrene tree Rouge, (methyl) acrylic resin, vinyl acetate resin, vinyl ethers system resin, halogen-containing resin, ester ring type alkene It is resin, polycarbonate-based resin, polyester based resin, polyamide resin, cellulose derivative, organic silicon-type resin and rubber Or elastomer etc..Above-mentioned thermoplastic resin is preferably amorphism and dissolves in organic solvent and (can especially dissolve 2 or more Polymer, curability compound general solvent).Particularly, from the aspect of as the transparency and weatherability, preferred benzene Vinylite, (methyl) acrylic resin, ester ring type olefin-based resin, polyester based resin, cellulose derivative (cellulose Esters etc.) etc..
Also, above-mentioned priming coat can also contain thermosetting resin.Such thermosetting resin is not particularly limited, it can It is poly- to enumerate such as phenol resin, carbamide resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturation Ester resin, polyurethane resin, epoxy resin, amino-alkyd resin, melamine-urea formaldehyde co-condensation resin, silicone resin, poly- silicon oxygen Alkane resin etc..
Priming coat containing above-mentioned particle a and binder resin a can be formed: for example, will contain above-mentioned particle A, the monomer component of binder resin a and the priming coat of solvent are coated on Mght-transmitting base material with composition, and drying forms film, Make the curing of coating by ionizing radiation exposure etc., priming coat is consequently formed.
As the solvent contained by above-mentioned priming coat composition, it can be cited for example that alcohols (such as methanol, ethyl alcohol, third Alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, benzyl alcohol, PGME, ethylene glycol), ketone (acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone etc.), ethers (dioxane, tetrahydrofuran etc.), aliphatic hydrocarbon (hexane etc.), ester ring type hydro carbons (ring Hexane etc.), aromatic hydrocarbon (toluene, dimethylbenzene etc.), halogenation carbons (methylene chloride, dichloroethanes etc.), esters (acetic acid first Ester, ethyl acetate, butyl acetate etc.), dioxane (methyl cellosolve, ethyl cellosolve etc.), cellosolve acetate class, sulfoxide type (dimethyl sulfoxide etc.), amides (dimethylformamide, dimethyl acetamide etc.) etc., are also possible to their mixture.
Above-mentioned priming coat composition preferably further contains Photoepolymerizationinitiater initiater.
Above-mentioned Photoepolymerizationinitiater initiater is not particularly limited, well known substance can be used, concrete example it can be cited for example that Acetophenones, benzophenone, michaelis benzoylbenzoic acid ester, α-pentoxime ester, thioxanthene ketone class, phenylpropyl alcohol ketone class, benzoin class, benzene Acyloin class, acylphosphine oxide class.And it is preferred that mixing photosensitizer is carried out using as its concrete example, it can be cited for example that positive fourth Amine, triethylamine, poly- normal-butyl phosphine etc..
As above-mentioned Photoepolymerizationinitiater initiater, above-mentioned binder resin a is the resin with free-radical polymerised unsaturated group In the case where system, preferably by acetophenones, benzophenone, thioxanthene ketone class, benzoin, benzoin methylether etc. individually or mixing make With.It is poly- as above-mentioned light also, in the case that above-mentioned binder resin a is the resin system with cationically polymerizable functional group Initiator is closed, preferably by aromatic diazonium salt, aromatic series sulfonium salt, aromatic iodonium salts, metallocene compound, benzoin sulphonic acid ester Deng being used alone or as a mixture use.
For the content of above-mentioned Photoepolymerizationinitiater initiater in above-mentioned priming coat composition, preferably with respect in 100 mass parts Stating binder resin a is 0.5~10.0 mass parts.When less than 0.5 mass parts, the hard painting propert of the priming coat of formation can may not fill Point, when being greater than 10.0 mass parts, it is likely to occur a possibility that obstruction solidifies instead, therefore not preferably.
Above-mentioned priming coat is not particularly limited with the raw material content ratio (solid component) in composition, usually 5~ 70 mass %, particularly, from the coating of above-mentioned priming coat composition it is appropriate from the aspect of preferably 20~60 mass %.It is right In above-mentioned priming coat composition, due to being to carry out several microns of thick coatings, if the too low (solvent contained of solid component Ratio it is high), then film is not easy drying, is formed by priming coat and is easy to appear film thickness unevenness.On the other hand, if above-mentioned priming coat Excessively high with the solid component of composition, then levelability is deteriorated, and is formed by priming coat and is easy to appear film thickness unevenness and deteriorated appearance.
It, can be according to the hardness, inhibition cure shrinkage, control refractive index for improving priming coat in above-mentioned priming coat composition The purpose of come add conventionally known dispersing agent, surfactant, antistatic agent, silane coupling agent, thickener, anti-coloring agent, It is colorant (pigment, dyestuff), defoaming agent, levelling agent, fire retardant, ultraviolet absorbing agent, bonding agent, polymerization inhibitor, anti-oxidant Agent, surface modifier etc..As levelling agent, such as silicone oil, fluorine class surfactant etc. due to can be avoided priming coat as shellfish Nader's eddy structure and it is preferred that.In the case that resin combination containing solvent is coated, is dried, in film, applying Film surface and inner face generate surface tension difference etc., and a large amount of convection current is thus caused in film.The structure quilt generated by the convection current Referred to as Bei Nade eddy structure will lead to and be formed by priming coat and orange peel, coating defects such problems occur.Shellfish Nader's whirlpool Structure can make the bumps on the surface of priming coat become excessive, may damage the appearance of hard coat film of the invention.Using it is above-mentioned that When the levelling agent of sample, the convection current can be prevented, can not only obtain that there is no defects and uneven priming coat, is also easy to primary coat The concaveconvex shape of layer surface is adjusted.
The preparation method of above-mentioned priming coat composition is not particularly limited, is as long as can uniformly mix each ingredient Can, can be used such as coating rocker, ball mill, kneader, mixer well known to device.
It is not particularly limited to above-mentioned priming coat is coated on the method on Mght-transmitting base material with composition, example can be enumerated Such as spin-coating method, infusion process, spray-on process, die coating method, stick coating method, rolling method, meniscus coating method, aniline printing method, silk-screen printing Method well known to method, drop rubbing method etc..After any painting bottom coating composition in the above method, in order to make shape At dried coating film and be sent to heated region, using various well known methods make dried coating film evaporate solvent.Herein may be used When with by solvent relative evaporation speed, solid component concentration, coating fluid temperature, drying temperature, the wind speed of dry wind, drying Between, the solvent atmosphere concentration of arid region etc. selected to adjust the distribution of the agglutination body of particle a.Particularly, pass through Select drying condition simple come the method for adjusting the distribution of particle a, so being preferred.It is excellent as specific drying temperature 30~120 DEG C are selected, dry wind speed is preferably 0.2~50m/s, at the drying by having been carried out suitable adjustment in the range It manages 1 time or for several times, the distribution of particle a can be adjusted to desired state.
Also, as the illuminating method of ionizing ray when making the curing of coating after above-mentioned drying, use example can be enumerated Such as method of ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc lamp, biuret light fluorescent lamp, metal halide lamp light source.And And the wavelength as ultraviolet light, the wave band of 190~380nm can be used.As the concrete example of electronic radial source, can enumerate Examine croft-Wa Erdun (Cockcroft-Walton) type, Van de Graaff type, resonance transformer type, insulating core transformer The various electron ray accelerators such as type or linear type, Dynamitron type, high-frequency type.
In hard coat film of the invention, above-mentioned priming coat is tried in the pencil hardness for example based on JIS K5600-5-4 (1999) It tests in (load 4.9N), hardness is preferably HB or more, 4H hereinafter, more preferably H or more.
The thickness of above-mentioned priming coat is preferably 0.5~8.0 μm.If thickness less than 0.5 μm, is unable to fully prevent oligomer Equal low molecular weight compositions are precipitated from above-mentioned Mght-transmitting base material, also, base coating surface may damage；If thickness is more than 8.0 μ M then may not only cannot achieve the filming of priming coat, but also priming coat is easy to split.The thickness of above-mentioned priming coat it is more excellent The range of choosing is 1.0~5.0 μm.It should be noted that the thickness of above-mentioned priming coat can be surveyed by cross sectional microscopy observation It is fixed.
Above-mentioned priming coat preferred index is 1.45~1.60.When the refractive index of above-mentioned priming coat is outside above range, with The refringence of Mght-transmitting base material etc. becomes the generation that significantly may cause interference fringe.
Hard coat film of the invention preferably has on the face of the side opposite with the face of priming coat side of above-mentioned Mght-transmitting base material There are other priming coats.By being able to suppress hard coat film of the invention and warpage, and energy occur with above-mentioned other priming coats Enough reduce the generation damaged in manufacturing process.Also, it is preferred that in the face phase with Mght-transmitting base material side of above-mentioned other priming coats Pair side face on the aftermentioned functional layer of lamination.In addition, it is above-mentioned others priming coat preferably have it is big with above-mentioned priming coat Cause identical surface unevenness profile.
Material same as above-mentioned priming coat can be used to be formed in above-mentioned others priming coat.By so being formed Above-mentioned others priming coat, can be improved the adhesion resistance of hard coat film of the invention and the effect of lubricity.
Hard coat film of the invention is preferably successively laminated with the high refractive index layer containing particle b and is contained on above-mentioned priming coat The low-index layer of particle c.
As described later, hard coat film of the invention preferably has through scheduled patterned conductive layer, but because is to be used for The component of contact panel sensor, therefore according to invisible etc. the requirement of above-mentioned patterned conductive layer, it is desirable that the present invention Hard coat film have strict optical characteristics.It is therefore desirable to which above-mentioned high refractive index layer and low-index layer are to thickness and refractive index Carry out strict control.Specifically, above-mentioned high refractive index layer preferred thickness is 10~100nm, refractive index is 1.55~1.75, Above-mentioned low-index layer preferred thickness is 10~100nm, refractive index is 1.35~1.55.Above-mentioned high refractive index layer and above-mentioned low folding The thickness for penetrating rate layer is more preferably 30~70nm.
In hard coat film of the invention, above-mentioned high refractive index layer, above-mentioned priming coat and above-mentioned low-index layer are preferably respective Refractive index meets the relationship of following formula (2).By meeting following formula (2), it can suitably realize and be formed on above-mentioned low-index layer Conductive layer it is invisible.
Refractive index > priming coat refractive index > low-index layer refractive index (2) of high refractive index layer
It should be noted that hard coat film of the invention can also wait positions to have adhesion below conductive layer The functional layers such as layer, inorganic layer.It will be described in more detail below for above-mentioned inorganic layer.
As above-mentioned high refractive index layer, it can be cited for example that the layer formed containing binder resin b and particle b.As Above-mentioned particle b can be suitable for the particle for selecting to have desired refractive index.The particle relatively high as refractive index, Ke Yiju Out for example with zinc oxide (1.90), titanium dioxide (2.3~2.7), cerium oxide (1.95), tin-doped indium oxide (1.95~ 2.00), antimony-doped tin oxide (1.75~1.85), yttrium oxide (1.87), zirconium oxide (2.10) etc. are the particle of raw material.It needs It is bright, the refractive index of the material of each particle is indicated in above-mentioned bracket.Wherein, as the above-mentioned preferred zirconia particles of particle b, on State in high refractive index layer, from a manner of density include particle b from the aspect of, it is micro- that particle b is more preferably amorphous zirconium Grain.By being not easy in high refractive index layer most close filling, the binder tree in the high refractive index layer for amorphous particulate zirconia The contact ratio of rouge a and low-index layer increases, to promote the raising of the adaptation of these interlayers.
The average grain diameter of above-mentioned particle b is preferably 15~50nm.If being less than 15nm, in order to improve above-mentioned high refractive index layer Refractive index and need to increase the additive amount of necessary particle b, also, due to above-mentioned particle b in above-mentioned high refractive index layer Disperse evenly, the state of above-mentioned density will not be become, the interlayer adaptation of high refractive index layer and low-index layer may be deteriorated. On the other hand, if more than 50nm, the biggish concaveconvex shape due to particle b is formed on the surface of above-mentioned high refractive index layer, In the case where forming aftermentioned conductive layer on low-index layer, be easy to appear the conductive layer film forming when crackle the disadvantages of, film Thickness ununiformity, it is difficult to realize low resistance, the fluctuation of resistance value may also become larger.The average grain diameter of above-mentioned particle b it is preferred Lower limit is 20nm, the preferred upper limit is 35nm.
Above-mentioned binder resin b is not particularly limited, such as thermoplastic resin can be used, from raising surface hardness From the aspect of, preferably by the curable resin compositions shape such as heat curing-type resin composition or ionizing radiation curable resin composition At wherein more preferably being formed by ionizing radiation curable resin composition.As above-mentioned heat curing-type resin composition, can enumerate Such as contain acrylic resin, carbamate resins, phenol resin, urea melmac, epoxy resin, unsaturated polyester (UP) Substance made of the gel-type resins such as resin, organic siliconresin and the curing agent added when necessary；Or it is above-mentioned solid containing constituting Substance made of the monomer and curing agent of change type resin etc..
As the ionizing radiation curable resin of above-mentioned ionizing radiation curable resin composition, acrylate can be enumerated The compounds with 1 or 2 or more unsaturated bond such as the compound of functional group of system or methacrylate ester.As in this way Compound, can enumerate same as the ionizing radiation curable resin that the binder resin as above-mentioned priming coat illustrated Compound.Also, these compounds can be halogen atom, sulphur, nitrogen, phosphorus atoms imported other than aromatic rings, fluorine etc. and will reflect Compound after rate height-regulating.
In addition, other than above compound, can also use the lower polyester resin of molecular weight with unsaturated double-bond, Polyether resin, acrylic resin, epoxy resin, carbamate resins, alkyd resin, spiral shell acetal resin, polybutadiene tree Rouge, polythiol-more olefine resins etc. are used as ionizing radiation curable resin composition.
Made in the cured situation of above-mentioned ionizing radiation curable resin composition by ultraviolet light irradiation, preferably the composition In contain the additives such as Photoepolymerizationinitiater initiater, photopolymerization promoter.As above-mentioned Photoepolymerizationinitiater initiater, it can be cited for example that benzene second Ketone, benzophenone, michler's ketone, benzoin, benzylmethylketal, benzoylbenzoic acid ester, α-acyl group oxime ester, alpha-alcohol ketone, Thioxanthene ketone class etc..In the present invention, from the high rigidity aspect of high refractive index layer and low-index layer, 2- hydroxyl -1- { 4- [4- (2- hydroxy-2-methyl propiono) benzyl] phenyl } -2- methylpropane -1- ketone is suitable.Also, above-mentioned photopolymerization promotees Polymerization obstacle caused by being air when can reduce as solidifying into agent, the substance for accelerating curing rate, it can be cited for example that right Dimethylaminobenzoic acid isopentyl ester, (dimethylamino)-ethyl benzoate etc..
In hard coat film of the invention, above-mentioned high refractive index layer contains preferably with respect to the above-mentioned binder resin b of 100 mass parts 100~300 mass parts of particle b.If the refractive index of above-mentioned high refractive index layer becomes inadequate less than 100 mass parts, if super 300 mass parts are crossed, then possibly can not be sufficiently formed above-mentioned particle b at the interface of above-mentioned high refractive index layer and above-mentioned low-index layer The interlayer adaptation of the region being not present with above-mentioned particle c, high refractive index layer and low-index layer may be deteriorated.Also, Since above-mentioned binder resin b ingredient is few, the combination effect of binder resin b dies down, and high refractive index layer is easily peeled off or hardness It is lower.The preferred lower limit of the content of above-mentioned particle b is 150 mass parts, the preferred upper limit is 250 mass parts.
As above-mentioned low-index layer, it can be cited for example that containing layer made of binder resin c and particle c.As upper Binder resin c is stated, the binder resin b enumerated in above-mentioned high refractive index layer can be used.Also, it can also mix and be imported with The low material of the refractive index such as resin, the organopolysiloxane of fluorine atom is as binder resin c.As in above-mentioned low-index layer Used in particle c, it can be cited for example that silicon dioxide microparticle, magnesium fluoride particulate or their hollow particle etc., preferably Silicon dioxide microparticle, more preferably colloidal silica particulate.By for colloidal silica particulate, from the side of dispersion stabilization Face is set out, when forming low-index layer it is preferable to use the colloidal solution for being dispersed with colloidal silicon dioxide in organic solvent, from It sets out in terms of the hardness for being formed by low-index layer, can be used further has the reaction of reactive functional groups on surface Property silica dioxide granule.The reactive silicon dioxide particle can constitute cross-linked structure between binder resin c, can make shape At the hardness of low-index layer become extremely excellent.
The average grain diameter of above-mentioned particle c is preferably 5nm less than 30nm.If being less than 5nm, may be susceptible to be aggregated, it can It can be difficult to use layer by layer in low-refraction evenly dispersed in composition.On the other hand, if more than 30nm, in above-mentioned low-index layer Surface on cannot form the above-mentioned concaveconvex shape c due to above-mentioned particle c for meeting above-mentioned parameter.Above-mentioned particle c's is flat The preferred lower limit of equal partial size is 10nm, the preferred upper limit is 15nm.
In hard coat film of the invention, above-mentioned low-index layer contains preferably with respect to the above-mentioned binder resin c of 100 mass parts 50~150 mass parts of particle c.If the refractive index of above-mentioned low-index layer becomes inadequate less than 50 mass parts.Another party Face, if more than 150 mass parts, the disadvantages of crackle when being easy to produce low-index layer film forming, film thickness it is uneven, it is difficult to realize and exist The low resistance of the conductive layer formed on low-index layer, and the fluctuation of the resistance value of conductive layer may also become larger.Also, by Binder resin c ingredient in low-index layer is few, and the combination effect of binder resin c dies down, and low-index layer is easy to shell It is lower from (not becoming low-index layer), hardness.The preferred lower limit of the content of above-mentioned particle c is 75 mass parts, more preferably The upper limit be 125 mass parts.
The face shape of the side opposite with the face of high refractive index layer side of the preferably above-mentioned low-index layer of hard coat film of the invention At there is conductive layer.The material for constituting above-mentioned conductive layer is not particularly limited, be suitable for using for example comprising selected from by indium, tin, zinc, The metal or metal of the metallic element of at least one of the group of gallium, antimony, titanium, silicon, zirconium, magnesium, aluminium, gold, silver, copper, palladium, tungsten composition Oxide.It can according to need metallic atom shown in further containing above-mentioned group in the metal oxide.For example, it is preferable to make With the indium oxide (ITO) containing tin oxide, tin oxide (ATO) containing antimony etc..
The thickness of above-mentioned conductive layer is not particularly limited, from ensure its sheet resistance be preferred 300 Ω/ or less, From the aspect of preferred 150 Ω/ good electric conductivity below, preferably 10nm or more, more preferably 15nm or more, Further preferably 20nm or more.On the other hand, above-mentioned by high refractive index layer and low-refraction if the thickness of conductive layer is excessive The layer sightless effect of bring may become smaller, and may generate the transparency reduces such inconvenience, therefore the thickness of conductive layer Preferably 60nm is spent hereinafter, more preferably 50nm is hereinafter, further preferably 40nm or less.
In hard coat film of the invention, in the case that above-mentioned conductive layer is made of above-mentioned metal oxide, above-mentioned conductive layer Refractive index be preferably 1.81 or more, more preferably 1.85 or more, further preferably 1.90 or more.The refraction of above-mentioned conductive layer The upper limit of rate is preferably 2.20 hereinafter, more preferably 2.10 or less.
The forming method of above-mentioned conductive layer is not particularly limited, conventionally known method can be used.Specifically, can To use the drying process such as vacuum vapour deposition, sputtering method, ion plating method.Also, it can also be used according to necessary film thickness Suitable method.It should be noted that in hard coat film of the invention, above-mentioned conductive layer lamination is in above-mentioned low-index layer (or tool Have the inorganic layer of the surface unevenness profile for the concaveconvex shape for substantially maintaining above-mentioned low-index layer) on, but example can also be passed through Above-mentioned conductive layer is such as formed on above-mentioned low-index layer etc. using sputtering method drying process, to make to be formed by conductive layer Surface have meet above-mentioned Rz and Ra relationship the concaveconvex shape a due to the particle a contained by above-mentioned priming coat.Cause This, can assign sufficient lubricity to conductive layer surface equal on low-index layer is formed in.In addition, in above-mentioned low-refraction In the case where being formed with the concaveconvex shape c for meeting above-mentioned parameter due to above-mentioned particle c on the surface of layer, the low-refraction The film-strength of layer can become excellent, can further realize the low resistance of above-mentioned conductive layer.Its reason will be aftermentioned.
Hard coat film of the invention is suitable for the contact panel sensor of electrostatic capacity, therefore above-mentioned conductive layer is preferred It is patterned.Such patterned conductive layer can be for example, by carrying out the conductive layer being film-made using the above method It patterns and obtains.It should be noted that passing through the patterning of above-mentioned conductive layer, drafting department and non-drafting department will form, as The shape of drafting department, it can be cited for example that striated, clathrate etc..
The patterning of above-mentioned conductive layer is usually carried out using etching.For example, utilizing lithoprinting on the electrically conductive After method, laser exposure method or print process form the anti-corrosion tunic of pattern-like, conductive layer pattern is made by etching process. As above-mentioned etching solution, conventionally known etching solution is used.Such as use the nothings such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid or phosphoric acid Machine acid；The organic acids such as acetic acid；Or their mixture；And these aqueous solution etc..
Above-mentioned conductive layer can according to need implementation heat treatment and be crystallized.By being crystallized to above-mentioned conductive layer Change, not only conductive layer meeting low resistance, can also improve the transparency and durability.It should be noted that being made by above-mentioned etching In the case where conductive layer pattern, if first carrying out the crystallization of conductive layer, it is likely difficult to be patterned using etching.Cause This, the heating anneal processing of conductive layer carries out preferably after making conductive layer pattern.
Herein, the surface of the preferably above-mentioned low-index layer of hard coat film of the invention is formed by due to above-mentioned particle c's Concaveconvex shape c meets above-mentioned scheduled parameter, and the flatness for meeting the concaveconvex shape c of such parameter is excellent, therefore at this In the case where forming inorganic layer on low-index layer, the film uniformity of the inorganic layer is got higher, and layer becomes flat.Such film Uniformity is high and flat inorganic layer in, barrier properties for gases is extremely excellent, lamination in the above-mentioned conductive layer on above-mentioned inorganic layer not Easily occur unevenness in the film of the conductive layer, as a result, distribution becomes good in the face of the resistance value of conductive layer, can be realized The low resistance of the conductive layer.
In hard coat film of the invention, above-mentioned conductive layer can be set to the two sides of above-mentioned Mght-transmitting base material.In this case, one A conductive layer across above-mentioned surface there is the low-index layer of scheduled concaveconvex shape to be set on above-mentioned Mght-transmitting base material, another Conductive layer can be directly arranged on above-mentioned Mght-transmitting base material, can also be set to above-mentioned translucency base across above-mentioned other priming coats On material.That is, above-mentioned others conductive layer, which can be directly arranged in, has scheduled bumps with the above-mentioned surface of above-mentioned Mght-transmitting base material On the face of the opposite side in the face of the low-index layer side of shape, the above-mentioned light transmission with above-mentioned other priming coats can also be set to On the face of the opposite side in the face of property substrate side.
Herein, in the case where the coiling body that aftermentioned such strip sheet is rolled into a roll being made in hard coat film of the invention, meeting The state directly contacted as said one conductive layer with another conductive layer.It is conductive when conductive layer so directly contacts each other The damage of layer mutual closely sealed (adhesive, lubricity) and the conductive layer in the case that above-mentioned conductive layer is made of metal material Problem can be become.In contrast, in hard coat film of the invention, it is formed with scheduled concaveconvex shape on the surface of above-mentioned conductive layer, Excellent adhesion resistance and lubricity are imparted, therefore even if is set to Mght-transmitting base material two sides in the case where coiling body is made Conductive layer mutual closely sealed (adhesive, lubricity) problem will not be become, additionally it is possible to effectively further prevent conductive layer Damage the problem of.
Hard coat film of the invention preferably forms inorganic layer between above-mentioned low-index layer side and above-mentioned conductive layer.Above-mentioned nothing Machine layer is played when being the hard coat film of the invention as manufacture and is prevented contained by above-mentioned priming coat, high refractive index layer and low-index layer The gas (vapor etc.) played the role of is transferred to the layer of conductive layer and the layer that functions.In hard coat film of the invention, pass through The vapor etc. contained by above-mentioned low-index layer etc. can suitably be prevented for above-mentioned conductive layer with above-mentioned inorganic layer Gases affect to conductive layer, get higher the resistance value of the conductive layer the phenomenon that.It should be noted that forming the feelings of above-mentioned inorganic layer Under condition, preferably it is formed on the surface of the inorganic layer and substantially maintains the bumps of the concaveconvex shape on surface of above-mentioned low-index layer Shape.Above-mentioned so-called " substantially maintaining the concaveconvex shape on the surface of low-index layer " is as described above.
In hard coat film of the invention, the material for constituting above-mentioned inorganic layer is not particularly limited, can be used existing known Material, it can be cited for example that silica, magnesium fluoride etc..It is wherein suitable for using silica.Also, above-mentioned inorganic layer can be with The surface of the side opposite with the face of high refractive index layer side of above-mentioned low-index layer is formed in using conventionally known method, it is right Its thickness etc. is not particularly limited.
The coiling body that strip sheet is rolled into a roll can be made in hard coat film of the invention.The strip sheet of hard coat film of the invention In coiling body, the web-like coiling body of strip sheet can be used as Mght-transmitting base material, above-mentioned priming coat, high refractive index layer, low folding It penetrates rate layer and conductive layer and passes through roll-to-roll method and formed.It, can be on the surface of hard coat film when forming such coiling body There is the protective film of weak adhesion coating to be then rolled into web-like as separating plate for upper adherency, but hard coat film of the invention is due to that can change Kind adhesion resistance and lubricity, therefore the winding of the strip sheet of hard coat film can be formed in the case where not using said protection film Body.
Hard coat film of the invention can be suitable for such as optical mode, ultrasonic wave mode, electrostatic capacity, resistive film side The contact panel sensor of formula etc., wherein the contact panel sensor of electrostatic capacity can be suitably adapted to.It is such Contact panel sensor with hard coat film of the invention is also one of present invention.
When forming contact panel sensor of the invention, can on one or two interarea of hard coat film of the invention every Other transparent bases of adhesion coating fitting glass or polymeric membrane etc. etc..For example, can the not formed low refraction on hard coat film Laminate is formed across transparent adhesion coating fitting transparent base on the face of the side of rate layer and conductive layer.Transparent base can be with It is made of 1 base film, or the laminates of 2 or more base films (such as formed across transparent adhesion coating lamination Laminate).Also, hard conating can also be set in the outer surface for the transparent base for fitting in hard coat film.
It is not particularly limited to for hard coat film with the adhesion coating of transparent base being bonded, as long as having the transparency. Specifically, can be suitable for selecting such as acrylic acid series polymeric compounds, silicone-based polymer, polyester, polyurethane, polyamide, poly- second Alkene ether, vinyl acetate/ethlyene dichloride copolymer, improved polyalkene, epoxy based polymer, fluorine-based polymer, natural rubber, conjunction At the substance that the polymer such as the rubber series such as rubber are basic polymer carry out using.Particularly, excellent from optical transparence；Display The adhesiveness such as wetability, compendency and the cementability of appropriateness；From the aspect of weatherability, heat resistance etc. are excellent, it is preferable to use Acrylic acid series sticker.
As described above, adhesion resistance and the excellent hard coat film of lubricity can be made in hard coat film of the invention, therefore can It is manufactured more effectively by roll-to-roll method.In turn, the low-index layer of hard coat film of the invention is that the bumps on surface are non- Often smooth shape, therefore the conductive layer of lamination thereon is difficult to generate unevenness in film, as a result, the resistance value of conductive layer Face in distribution become good.
(preferred embodiment)
, it is preferable to use sweep type white Gan Wataru microscope is in measurement visual field 0.12mm measurement in hard coat film of the invention 10 mean roughness of the concaveconvex shape of above-mentioned low-index layer are the concave-convex of 50~500nm and above-mentioned low-index layer The arithmetic average roughness of shape is 0.5~10.0nm, also, it is preferable to use scanning type probe microscopes in measurement 5 μm of visual field 10 mean roughness of the concaveconvex shape of the above-mentioned low-index layer of measurement are the recessed of 50nm or less and above-mentioned low-index layer The arithmetic average roughness of convex form is 3.0nm or less.
Also, it is preferred that above-mentioned priming coat contains particle a, above-mentioned high refractive index layer contains particle b, above-mentioned low-index layer contains There is particle c, the average grain diameter of above-mentioned particle a is 0.1~3.0 μm, the average grain diameter of above-mentioned particle b is 15~50nm and above-mentioned The average grain diameter of particle c is 5nm less than 30nm.
Also, it is preferred that the above-mentioned particle a that above-mentioned priming coat contains is that silicon dioxide microparticle, above-mentioned high refractive index layer contain Above-mentioned particle b is that the above-mentioned particle c that zirconia particles and above-mentioned low-index layer contain is silicon dioxide microparticle.
Also, it is preferred that the above-mentioned particle a that above-mentioned priming coat contains is spherical silicon dioxide particulate or colloidal silicon dioxide The above-mentioned particle b that particle, above-mentioned high refractive index layer contain is amorphous particulate zirconia and above-mentioned low-index layer contain it is upper Stating particle c is colloidal silica particulate.
Also, it is preferred that being formed with above-mentioned particle b and above-mentioned at the interface of above-mentioned high refractive index layer and above-mentioned low-index layer The region that particle c is not present.
Also, the refractive index of the preferably above-mentioned priming coat of hard coat film of the invention is 1.45~1.60, above-mentioned high refractive index layer Refractive index be 1.55~1.75, the refractive index of above-mentioned low-index layer is 1.35~1.55 and above-mentioned high refractive index layer, above-mentioned Priming coat and the respective refractive index of above-mentioned low-index layer meet the relationship of following formula (2).
Refractive index > priming coat refractive index > low-index layer refractive index (2) of high refractive index layer
Also, hard coat film of the invention is preferably in the opposite with the face of above-mentioned high refractive index layer side of above-mentioned low-index layer The face of side is formed with conductive layer.
Also, hard coat film of the invention preferably further has to be formed between above-mentioned low-index layer and above-mentioned conductive layer Inorganic layer.
[embodiment 1]
The 1st mode in order to explain the present invention in detail, following examples are given to illustrate, but the present invention is not limited to this It is a little to record.
<preparation of priming coat composition>
Firstly, each ingredient of composition mixture as described below, obtains priming coat composition.
(priming coat composition)
Pentaerythritol triacrylate (PETA): 30 mass parts
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 1.5 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.05 mass parts
Methyl iso-butyl ketone (MIBK): 70 mass parts
<preparation of high refractive index layer composition>
Each ingredient of composition mixture as described below, obtains high refractive index layer composition.
(high refractive index layer composition 1-1)
High refractive index particle dispersion (ZrO2The methyl ethyl ketone dispersion (solid component: 32.5 mass %) of particle, ProductName " MZ-230X ", Sumitomo Osaka Cement Co., ltd. manufacture): 51.0 mass parts
Pentaerythritol triacrylate (ProductName " KAYARAD PET-30 ", manufactured by Japan Chemical Drug Society): 19.4 mass Part
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 0.6 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.03 mass parts
Methyl iso-butyl ketone (MIBK) (MIBK): 1129.6 mass parts
(high refractive index layer composition 1-2)
High refractive index particle dispersion (ZrO2The methyl ethyl ketone dispersion (solid component: 32.5 mass %) of particle, ProductName " MZ-230X ", Sumitomo Osaka Cement Co., ltd. manufacture): 44.3 mass parts
Pentaerythritol triacrylate (ProductName " KAYARAD PET-30 ", manufactured by Japan Chemical Drug Society): 21.6 mass Part
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 0.6 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.03 mass parts
Methyl iso-butyl ketone (MIBK) (MIBK): 1134.1 mass parts
(high refractive index layer composition 1-3)
High refractive index particle dispersion (ZrO2The methyl ethyl ketone dispersion (solid component: 32.5 mass %) of particle, ProductName " MZ-230X ", Sumitomo Osaka Cement Co., ltd. manufacture): 70.9 mass parts
Pentaerythritol triacrylate (ProductName " KAYARAD PET-30 ", manufactured by Japan Chemical Drug Society): 13.0 mass Part
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 0.6 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.03 mass parts
Methyl iso-butyl ketone (MIBK) (MIBK): 1116.1 mass parts
(high refractive index layer composition 1-4)
High refractive index particle dispersion (ZrO2The methyl ethyl ketone dispersion (solid component: 32.5 mass %) of particle, ProductName " MZ-230X ", Sumitomo Osaka Cement Co., ltd. manufacture): 15.8 mass parts
Pentaerythritol triacrylate (ProductName " KAYARAD PET-30 ", manufactured by Japan Chemical Drug Society): 62.0 mass Part
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 0.6 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.03 mass parts
Methyl iso-butyl ketone (MIBK) (MIBK): 200 mass parts
(high refractive index layer composition 1-5)
High refractive index particle dispersion (ZrO2The methyl ethyl ketone dispersion (solid component: 32.5 mass %) of particle, ProductName " MZ-230X ", Sumitomo Osaka Cement Co., ltd. manufacture): 37.7 mass parts
Pentaerythritol triacrylate (ProductName " KAYARAD PET-30 ", manufactured by Japan Chemical Drug Society): 23.8 mass Part
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 0.6 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.03 mass parts
Methyl iso-butyl ketone (MIBK) (MIBK): 1138.6 mass parts
(high refractive index layer composition 1-6)
High refractive index particle dispersion (ZrO2The methyl ethyl ketone dispersion (solid component: 32.5 mass %) of particle, ProductName " MZ-230X ", Sumitomo Osaka Cement Co., ltd. manufacture): 90.8 mass parts
Pentaerythritol triacrylate (ProductName " KAYARAD PET-30 ", manufactured by Japan Chemical Drug Society): 6.5 mass parts
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 0.6 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.03 mass parts
Methyl iso-butyl ketone (MIBK) (MIBK): 1102.7 mass parts
<preparation of composition for low refractive index layer>
Each ingredient of composition mixture as described below, obtains composition for low refractive index layer.
(composition for low refractive index layer 1-1)
Low refractive index particle dispersion liquid (MIBK-SD (methyl iso-butyl ketone (mibk) dispersion liquid of silicon dioxide microparticle, solid at Divide 30% dispersion liquid (solid component: 30.0 mass %), ProductName " MIBK-SD ", the manufacture of Nissan Chemical Industries society)): 15 mass Part
Pentaerythritol triacrylate (manufactured by Japan Chemical Drug Society, KAYARAD-PET-30): 5 mass parts
Photoepolymerizationinitiater initiater (manufacture of BASF society, Irgacure 184): 1 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, SEIKA-BEAM10-28, solid component 10%): 0.2 matter Measure part
Methyl iso-butyl ketone (MIBK): 1000 mass parts
(composition for low refractive index layer 1-2)
Pentaerythritol triacrylate (PETA): 30 mass parts
Polymerization initiator (ProductName " Irgacure 184 ", the manufacture of BASF Japan society): 1.5 mass parts silicone-baseds Levelling agent (industrial society's manufacture of refining big day, ProductName " SEIKA-BEAM10-28 ", solid component 10%): 0.05 mass parts
Methyl iso-butyl ketone (MIBK): 1000 mass parts
<embodiment 1-1>
Prepare polyethylene terephthalate substrate (ProductName " Cosmoshine ", Japan's spinning with a thickness of 125 μm Society's manufacture) it is used as Mght-transmitting base material, high refractive index layer combination is coated on the single side of polyethylene terephthalate substrate Object 1-1 forms film.Next, making to be formed by film after 40 DEG C 1 minute dry, in nitrogen atmosphere (oxygen concentration 200ppm It with accumulated light is 100mJ/cm under below)2Mode carry out ultraviolet light irradiation, make curing of coating, refractive index, which is consequently formed, is 1.60 and film thickness be 60nm high refractive index layer.Next, in high-frequency sputtering device, to electrode apply frequency 13.56MHz, The RF power of electric power 5kW, makes it discharge in chamber, is formed on high refractive index layer and is made of target material (silica) Refractive index be 1.46 and low-index layer that film thickness is 25nm.Next, forming tin on low-index layer using sputtering method Doped indium oxide (ITO) layer, carries out heating for 30 minutes in 150 DEG C of heated oven, is allowed to crystallize.Then photograph is utilized Phase lithography will be formed by ITO layer patterning, form that refractive index is 1.98 and film thickness is the patterned of 25nm Thus bright conductive layer produces the conductive film of embodiment 1.
<embodiment 1-2>
Prepare polyethylene terephthalate substrate (ProductName " Cosmoshine ", Japan's spinning with a thickness of 125 μm Society's manufacture) it is used as Mght-transmitting base material, painting bottom coating composition, shape on the single side of polyethylene terephthalate substrate At film.Next, against film is formed by with after dry air 15 seconds of 50 DEG C of flow rate of 0.2m/s, further with Dry air 30 seconds of 70 DEG C of flow rate of 10m/s, are allowed to drying, thus evaporate the solvent in film, in nitrogen atmosphere It with accumulated light is 100mJ/cm under (oxygen concentration 200ppm or less)2Mode irradiate ultraviolet light, make curing of coating, be consequently formed The priming coat that refractive index is 1.52 and film thickness is 2.0 μm.Next, high refractive index layer composition 1-1 is coated on priming coat, Form film.Then, film will be formed by after 40 DEG C 1 minute dry, under nitrogen atmosphere (oxygen concentration 200ppm or less) With 100mJ/cm2Accumulated light carry out ultraviolet light irradiation, be allowed to solidify, form the height that refractive index is 1.60 and film thickness is 60nm Index layer.Next, apply the RF power of frequency 13.56MHz, electric power 5kW to electrode in high-frequency sputtering device, by This makes it discharge in chamber, and it is 1.46 Hes that the refractive index being made of target material (silica) is formed on high refractive index layer Film thickness is the low-index layer of 25nm.Next, tin-doped indium oxide (ITO) is formed on low-index layer using sputtering method Layer, carries out heating for 30 minutes in 150 DEG C of heated oven, is allowed to crystallize.Then utilize photolithography will It is formed by ITO layer patterning, the patterned transparency conducting layer that refractive index is 1.98 and film thickness is 25nm is formed, thus makes Make the conductive film of embodiment 2.
<embodiment 1-3>
In embodiment 1-3, other than making the film thickness of the film thickness 30nm of high refractive index layer, low-index layer be 10nm, Implement in the same manner as embodiment 1-1, produces conductive film.
<embodiment 1-4>
In embodiment 1-4, other than making the film thickness of the film thickness 30nm of high refractive index layer, low-index layer be 40nm, Implement in the same manner as embodiment 1-1, produces conductive film.
<embodiment 1-5>
In embodiment 1-5, other than the composition of low-index layer and forming method, implement in the same manner as embodiment 1-1, Produce conductive film.In embodiment 1-5, composition for low refractive index layer 1-1 is coated on high refractive index layer and forms film, it will Film is formed by after 40 DEG C 1 minute dry, with 100mJ/cm at nitrogen atmosphere (oxygen concentration 200ppm or less)2Accumulation Light quantity carries out ultraviolet light irradiation, is allowed to solidify, forms the low-index layer that refractive index is 1.49 and film thickness is 25nm.
<embodiment 1-6>
In embodiment 1-6, other than the film thickness 40nm for making transparency conducting layer, implement in the same manner as embodiment 1-5, makes Make conductive film.
<embodiment 1-7>
In embodiment 1-7, high refractive index layer composition 1-2 is used without using high refractive index layer composition 1-1, is made The film thickness of low-index layer is that 40nm implements in the same manner as embodiment 1-5 in addition to this, produces conductive film.Embodiment 1- The refractive index of the high refractive index layer of 7 conductive film is 1.57.
<embodiment 1-8>
In embodiment 1-8, high refractive index layer composition 1-3 is used without using high refractive index layer composition 1-1, is made The layer being made of magnesium fluoride is formed for low-index layer to implement in the same manner as embodiment 1-1 in addition to this, produce electric conductivity Film.The refractive index of the high refractive index layer of the conductive film of embodiment 1-8 is 1.67, and the refractive index of low-index layer is 1.38.
<embodiment 1-9>
In embodiment 1-9, high refractive index layer composition 1-3 is used without using high refractive index layer composition 1-1, no Composition for low refractive index layer 1-2 is used using composition for low refractive index layer 1-1, it is in addition to this, same as embodiment 1-5 Ground is implemented, and conductive film is produced.The refractive index of the high refractive index layer of the conductive film of embodiment 1-9 is 1.67, low-refraction The refractive index of layer is 1.52.
<embodiment 1-10>
In embodiment 1-10, high refractive index layer composition 4 is used without using high refractive index layer composition 1-1, is made The film thickness of high refractive index layer is that 1200nm implements in the same manner as embodiment 1-5 in addition to this, produces conductive film.Embodiment The refractive index of the high refractive index layer of the conductive film of 1-10 is 1.63.
<embodiment 1-11>
In embodiment 1-11, other than the film thickness 80nm for making high refractive index layer, implement in the same manner as embodiment 1-5, Produce conductive film.
<embodiment 1-12>
In embodiment 1-12, high refractive index layer composition 1-3 is used without using high refractive index layer composition 1-1, The film thickness of the film thickness 30nm, low-index layer that make high refractive index layer are 60nm, in addition to this, real in the same manner as embodiment 1-5 It applies, produces conductive film.
<comparative example 1-1>
In comparative example 1-1, in addition to without using high refractive index layer composition 1 and use high refractive index layer composition 5 with Outside, implement in the same manner as embodiment 1-1, produce conductive film.The refraction of the high refractive index layer of the conductive film of comparative example 1-1 Rate is 1.54.
<comparative example 1-2>
In comparative example 1-2, high refractive index layer composition 1-6 is used without using high refractive index layer composition 1-1, is removed Other than this, implements in the same manner as embodiment 1-1, produce conductive film.The high refractive index layer of the conductive film of comparative example 1-2 Refractive index is 1.76.
The composition of obtained conductive film in embodiment 1-1~1-12 and comparative example 1-1 and 1-2 is summarized in table 1.
[table 1]
<fluctuation of a* and b*>
In each intermediate substrate film obtained in examples and comparative examples, the fluctuation of a* and b* are found out as follows.Specifically It says, the VAR-7010 manufactured using Japan Spectroscopy Corporation, is irradiated by the ITO layer of each conductive film of the surface lateral of ITO layer Light, while every 5 ° of ground transformation incident angle in the range of 5 °~75 °, are obtained by the respective reflected light towards mirror-reflection direction To a* value and b* value.Determination condition is as follows.Light source is tilted using heavy hydrogen (D2) lamp and plain (WI) lamp of tungsten halogen using transmission axis Measurement range is set as 380nm~780nm by 45 ° of polarizer, and reading data interval is set as 1nm, make when being measured into Firing angle degree is synchronous with the position of detector so as to reading in specular light.Then, according under obtained each incident angle A* value and b* value, calculate the absolute value of the difference of its maxima and minima, thus find out a* value fluctuation and b* value wave It is dynamic.
<fluctuation of tone>
The color of each conductive film when for each conductive film obtained in viewing embodiment at various orientations and comparative example It adjusts with the presence or absence of fluctuation to be evaluated.Evaluation criteria is as follows.
Zero: the fluctuation of tone is not confirmed.
×: confirm the fluctuation of tone.
Result is listed in 2~table of table 4 below.
[table 4]
The fluctuation of a* value The fluctuation of b* value The fluctuation of tone
Embodiment 1-1 1.41 2.46 ○
Embodiment 1-2 1.43 2.28 ○
Embodiment 1-3 0.95 6.19 ○
Embodiment 1-4 0.95 6.02 ○
Embodiment 1-5 1.32 2.02 ○
Embodiment 1-6 1.46 5.35 ○
Embodiment 1-7 1.65 6.97 ○
Embodiment 1-8 3.16 4.62 ○
Embodiment 1-9 2.57 4.42 ○
Embodiment 1-10 0.29 4.87 ○
Embodiment 1-11 2.94 5.74 ○
Embodiment 1-12 2.28 4.14 ○
Comparative example 1-1 1.01 7.06 ×
Comparative example 1-2 4.79 13.62 ×
As shown in table 4, it is within 3.5 and b* value that the conductive film of comparative example 1-1 and 1-2, which is unsatisfactory for the fluctuation of a* value, Fluctuation is the condition within 7.0, therefore could not inhibit the fluctuation of tone.
In contrast, the conductive film of embodiment 1-1~1-12 meet a* value fluctuation be 3.5 within and b* value wave Moving is condition within 7.0, therefore is able to suppress the variation of tone.
[embodiment 2]
For the 2nd mode that the present invention will be described in detail, following examples are given to illustrate, but the present invention is not restricted to these It records.
(embodiment 2-1)
In the biaxial stretching polyester film with a thickness of 100 μm, (society A4300 spins in Japan；With precoated shet) a face on be coated with The priming coat coating fluid of following formulas so that after dry with a thickness of 1.5 μm, carry out the drying and ultraviolet light irradiation of film, shape At priming coat (refractive index 1.52, pencil hardness H).It should be noted that ultraviolet irradiation amount is 300mJ/cm2, film Drying condition is 70 DEG C, 60 seconds.Also, on another face of above-mentioned biaxial stretching polyester film, use the primary coat of following formulas Layer coating fluid forms priming coat according to condition identical with the priming coat being formed on said one face, next, with series connection The mode of (イ Application ラ イ Application) continuously forms high refraction on the priming coat in another face for being formed in biaxial stretching polyester film Rate layer (thickness 50nm, refractive index 1.66) and low-index layer (thickness 30m, refractive index 1.49), obtain hard coat film.It needs to illustrate , the coating fluid of high refractive index layer and low-index layer uses following substance.The drying condition of high refractive index layer is 50 DEG C, 60 Second, the drying condition of low-index layer is 50 DEG C, 60 seconds.Also, to each layer of priming coat, high refractive index layer and low-index layer After being dried, ultraviolet light irradiation (100mJ/cm2) is carried out respectively.
(sputtering condition)
In the atmosphere for the 0.5Pa being made of 99 capacity % of argon gas and 1 capacity % of oxygen, added with 100 DEG C of condition of temperature Heat, while with the output power that discharges: the transparency conducting layer that the condition of 5W/cm2 is formed using reactive sputtering method with a thickness of 25nm (refractive index of light is 2.00).
<priming coat coating fluid>
Dipentaerythritol hexaacrylate (manufactured by Japan Chemical Drug Society, DPHA) 50 mass parts
Photoepolymerizationinitiater initiater (manufacture of BASF society, Irgacure 184) 2 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, SEIKA-BEAM 10-28, solid component 10%) 0.1 mass Part
Particle a contains 0.3 mass parts of liquid
60 mass parts of methyl iso-butyl ketone (MIBK)
15 mass parts of cyclohexanone
It should be noted that particle a contain liquid be by acrylic resin particle (it is comprehensive to grind the manufacture of chemical society, MX-180TA, 1.8 μm of average grain diameter) it is scattered in the substance that solid component obtained in methyl iso-butyl ketone (MIBK) is 15%.
<high refractive index layer coating fluid>
Pentaerythritol triacrylate (manufactured by Japan Chemical Drug Society, KAYARAD-PET-30) 10 mass parts
Photoepolymerizationinitiater initiater (manufacture of BASF society, Irgacure 127) 0.7 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, SEIKA-BEAM 10-28, solid component 10%) 0.3 mass Part
Particle b contains 50 mass parts of liquid
500 mass parts of methyl iso-butyl ketone (MIBK)
250 mass parts of cyclohexanone
500 mass parts of methyl ethyl ketone
It should be noted that particle b contains MZ-230X (the zirconium oxide dispersion that liquid has used Sumitomo Osaka Cement Co., ltd. to manufacture Liquid, solid component 32.5%, average grain diameter 27nm).
<low-index layer coating fluid>
Pentaerythritol triacrylate (manufactured by Japan Chemical Drug Society, KAYARAD-PET-30) 5 mass parts
Photoepolymerizationinitiater initiater (manufacture of BASF society, Irgacure 127) 1 mass parts
Silicone-based levelling agent (industrial society's manufacture of refining big day, SEIKA-BEAM 10-28, solid component 10%) 0.2 mass Part
Particle c contains 15 mass parts of liquid
1000 mass parts of methyl iso-butyl ketone (MIBK)
250 mass parts of cyclohexanone
It should be noted that particle c contains the MIBK-SD that liquid has used Nissan Chemical Industries society to manufacture, (silica is micro- Grain dispersion liquid, solid component 30%, average grain diameter 15nm).
(embodiment 2-2)
It is real in the same manner as embodiment 2-1 other than the combined amount of the particle a of embodiment 2-1 is changed to 1.0 mass parts It applies, obtains hard coat film.
(embodiment 2-3)
The particle a of embodiment 2-1 is changed to the MIBK-SD-L (silicon dioxide microparticle point of Nissan Chemical Industries society manufacture Dispersion liquid, solid component 30%, average grain diameter 15nm) solid component that is dispersed with methyl iso-butyl ketone (MIBK) be 15% substance, Combined amount is changed to 17 mass parts, in addition to this, implements in the same manner as embodiment 2-1, obtains hard coat film.
(embodiment 2-4)
It is real in the same manner as embodiment 2-1 other than the combined amount of the particle a of embodiment 2-3 is changed to 34 mass parts It applies, obtains hard coat film.
(comparative example 2-1)
Particle a is removed from the priming coat coating fluid of embodiment 2-1, and 1.4 mass are added in high refractive index layer coating fluid The ProductName " SIRMIBK-H84 " (solid component 30%) of part CIK Nano Tek society manufacture is used as particle, in addition to this, with reality It applies a 2-1 similarly to implement, obtains hard coat film.
(reference example 2-1)
The particle a of embodiment 2-1 is changed to MIBK-SD-L (the silicon dioxide microparticle dispersion of Nissan Chemical Industries society manufacture Liquid, solid component 30%, average grain diameter 15nm) solid component that is dispersed with methyl iso-butyl ketone (MIBK) be 15% substance, will Combined amount is changed to 100 mass parts, in addition to this, implements in the same manner as embodiment 2-1, obtains hard coat film.
<physical property measurement of hard coat film and evaluation>
Physical property measurement and evaluation are carried out to hard coat film obtained in embodiment, comparative example and reference example as follows.Respective knot Fruit is listed in table 5.
[surface shape]
In the case where the visual field (measurement area) is measured as 0.12mm, it is based on passing through sweep type white interference microscope The data of the surface shape of (manufacture of Zygo society, trade name New View 6300) measurement calculate, obtained optical laminate Low-index layer Ra and Rz.The average value of measured value at each 10 is listed in table 1.Also, measure the visual field (measurement area) In the case where for 5 μm of, based on the surface shape measured by scanning type probe microscope (Shimadzu Seisakusho Ltd. SPM-9600) Data calculate, the Ra and Rz of the low-index layer of obtained optical laminate.By the average value of the measured value at each 10 It is listed in table 5.
[adhesion resistance]
Hard coat film obtained in each embodiment, comparative example and reference example is cut into the size of 5cm × 5cm respectively.By one The side for being provided only with priming coat of hard coat film and the low-index layer side opposite direction of another hard coat film are stacked, with pressure 3.0kgf/ After closely sealed 30 hours of cm2,50 DEG C of condition, evaluated using following benchmark.
Zero: nonadherent
×: there is adherency
[lubricity evaluation]
Hard coat film obtained in each embodiment, comparative example and reference example is cut into the size of 10cm × 10cm respectively.By one The side for being provided only with priming coat of a hard coat film and the low-index layer side opposite direction of another hard coat film are stacked, are confirmed by friction Sliding property utilizes following benchmark evaluation lubricities.
Zero: sliding property is good, no adherency, and lubricity is good.
×: sliding property is insufficient, and part adheres to, and lubricity is bad.
[surface resistivity]
To carrying out following conditions on the low-index layer of hard coat film obtained in each embodiment, comparative example and reference example Sputtering forms the transparency conducting layer (thickness 25nm) being made of indium tin oxide (ITO).Thereafter, 150 DEG C of 30 minutes move back are carried out Fire processing, formation conductive layer, the surface resistivity meter manufactured using society of Mitsubishi Chemical (MCP: four terminal probe of low-resistivity instrument), according to Sheet resistance is measured according to JIS R1637 (the resistivity test method of special cermacis film: the measuring method based on 4 sonde methods) Rate is evaluated using following benchmark.
Zero: surface resistivity is less than 150 Ω/
×: surface resistivity is 150 Ω/ or more
[visibility (gonorrhoea sense)]
By transparent adhesive, by each hard coat film obtained in each embodiment, comparative example and reference example and low-refraction The opposite face paste of layer observes gonorrhoea sense under desk lamp (3 wavelength fluorescent fluorescent tube) in darkroom, utilizes following base in black acrylic board Standard is evaluated.
Zero: not observing white.
×: observe white.
As shown in table 5, arithmetic average roughness (Ra) of the hard coat film of embodiment in the big visual field (visual field 0.12mm) The range of 50~500nm is in for 0.5~10.0nm, 10 mean roughness (Rz), the Ra in micro- visual field (5 μm of visuals field) For 3.0nm or less, Rz be 50nm hereinafter, Ra and Rz in the big visual field be greater than the value of Ra and Rz in micro- visual field, therefore it is resistance to Adhesive is excellent without damaging gonorrhoea sense, in addition, the film forming of conductive layer is good, the disadvantages of without crackle and film thickness is uneven, Resistance value is low.
On the other hand, the hard coat film of comparative example 2-1 does not contain particle a, and conductive layer surface is not sufficiently formed the big visual field (concaveconvex shape a), Ra and Rz in the big visual field are less than in micro- visual field (5 μm of visuals field) concaveconvex shape under (visual field 0.12mm) Ra and Rz, could not realize adhesion resistance, lubricity and low resistance value.
Also, in the hard coat film of reference example 2-1, the Ra and Rz in the big visual field (visual field 0.12mm) are very big, respectively 10.5nm, 543nm, and the Ra in micro- visual field (5 μm of visuals field) is also greatly to 4.5nm, therefore the film forming of conductive layer deteriorates, and produces The disadvantages of having given birth to crackle and film thickness are uneven, as a result could not realize low resistance, and visibility is also poor.
[industrial applicibility]
Hard coat film of the invention can suitably be applied to the touch-control of contact panel sensor, especially electrostatic capacity Panel sensors.
[symbol description]
10,21,40,60,70 ... conductive film
The surface 10A, 40A, 60A, 70A ...
11 ... Mght-transmitting base materials
12,13 ... priming coats
14,41,61,71 ... high refractive index layer
15,42,62,72 ... low-index layer
16,22,32,43,63,73 ... transparency conducting layer
20,30,50 ... contact panel sensor

Claims (8)

1. a kind of conductive film, includes
Mght-transmitting base material,
Lamination in the one or two sides of the Mght-transmitting base material high refractive index layer,
Lamination is on the high refractive index layer and the low-index layer of refractive index of the refractive index lower than the high refractive index layer, lamination In on the low-index layer and patterned transparency conducting layer,
The transparency conducting layer irradiation light as described in the surface lateral of the transparency conducting layer, and set the method on the surface of the conductive film Line direction is 0 °, every 5 degree converts incident angle in 5 ° or more 75 ° or less of range and is irradiated, by respective towards mirror The reflected light of face reflection direction finds out L*a*b*The a of colorimeter system*Value and b*When value, a*The fluctuation of value is and b within 3.5*Value Fluctuation within 7.0,
The refractive index of the high refractive index layer be 1.57 or more 1.67 hereinafter,
The refractive index of the low-index layer be 1.35 or more 1.55 hereinafter,
Do not have priming coat between the Mght-transmitting base material and the high refractive index layer.
2. conductive film as described in claim 1, wherein the refringence of the high refractive index layer and the low-index layer It is 0.10 or more 0.30 or less.
3. conductive film as described in claim 1, wherein the high refractive index layer has 20nm or more 100nm film below Thick and 1.57 or more 1.67 refractive index below, and the low-index layer have 3nm or more 100nm film thickness below and 1.35 or more 1.55 refractive index below.
4. conductive film as described in claim 1, wherein the high refractive index layer has 0.5 μm or more 10 μm of films below Thick and 1.57 or more 1.67 refractive index below, and the low-index layer have 3nm or more 100nm film thickness below and 1.35 refractive index more than and less than 1.55.
5. conductive film as described in claim 1, wherein the transparency conducting layer has 15nm or more 50nm film thickness below With 1.85 or more 2.30 refractive index below.
6. conductive film as described in claim 1, wherein the transparency conducting layer is tin-doped indium oxide layer.
7. conductive film as described in claim 1, wherein a*The fluctuation of value is within 1.5.
8. a kind of contact panel sensor, wherein the contact panel sensor has conductive film described in claim 1.
CN201410662938.XA 2013-11-20 2014-11-19 Conductive film, hard coat film and contact panel sensor Active CN104656974B (en)

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