CN103959105A - Color tone correction film and transparent conductive film using same - Google Patents
Color tone correction film and transparent conductive film using same Download PDFInfo
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- CN103959105A CN103959105A CN201380004004.0A CN201380004004A CN103959105A CN 103959105 A CN103959105 A CN 103959105A CN 201380004004 A CN201380004004 A CN 201380004004A CN 103959105 A CN103959105 A CN 103959105A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0025—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration
- G02B27/005—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for optical correction, e.g. distorsion, aberration for correction of secondary colour or higher-order chromatic aberrations
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/206—Filters comprising particles embedded in a solid matrix
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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Abstract
In this color tone correction film, a first hard coat layer, a first color tone correction layer and a second color tone correction layer are sequentially laminated on one surface of a transparent base film, and a second hard coat layer is laminated on the other surface of the transparent base film. The second hard coat layer contains 80-98 wt% of a binder, 1-10 wt% of a photopolymerization initiator and 0.01-19 wt% of organic fine particles having an average particle diameter of 0.8-5.5 [mu]m. The second hard coat layer has a refractive index of 1.51-1.61 with respect to light having a wavelength of 400 nm, while having a film thickness of 1.3-3.5 [mu]m. The average particle diameter of the organic fine particles is 61-350% of the film thickness of the second hard coat layer, and the sum of the binder, the photopolymerization initiator and the organic fine particles having an average particle diameter of 0.8-5.5 [mu]m is 99-100 wt%.
Description
Technical field
The present invention relates to tint correction film and the transparent and electrically conductive film that possesses transparency conducting layer on tint correction film for a kind of contact panel.
Background technology
At present, contact panel, as carrying out the device of input message by direct touch image displaying part, is widely used.Contact panel is that the input media that sees through light is configured in to the product on the display screens such as liquid crystal indicator, as the form of representative, has capacitance type touch-control panel, and it has utilized the variation of the current capacity producing between transparency electrode and finger.
The transparent and electrically conductive film of using as contact panel, the general use transparent and electrically conductive film that lamination transparency conducting layer forms on transparent base film, this transparency conducting layer is to consist of metal oxides such as the indium oxide that contains tin oxide (tin-doped indium oxide, ITO) or zinc paste.This transparent and electrically conductive film, because reduce from the transmitance in the reflection of metal oxide layer and the visible ray short wavelength region of absorption, when total light transmittance reduces, mostly can be observed and presents yellow.Therefore, there is the problem that is difficult to accurately show the color that the display device that is configured under contact panel is shown.
In order to address this problem, propose to have the transparent and electrically conductive film (referring to TOHKEMY 2011-98563 communique) that transparency conducting layer and multi-layer optical film are combined.The transparent and electrically conductive film of recording in TOHKEMY 2011-98563 communique starts lamination high refractive index layer, low-index layer and tin-doped indium oxide layer successively from the surface of the polyester film as transparent base film and forms.High refractive index layer is formed by metal oxide microparticle and ultraviolet-curing adhesive, and refractive index when optical wavelength is 400nm is 1.63～1.86, thickness is 40～90nm.The refractive index of low-index layer when optical wavelength is 400nm is 1.33～1.53, thickness is 10～50nm.The refractive index of tin-doped indium oxide layer when optical wavelength is 400nm is 1.85～2.35, thickness is 5～50nm.By above-mentioned formation, realize and reduce the effect that sees through optical colour.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2011-98563 communique
Summary of the invention
The technical matters that invention will solve
Here, the transparent and electrically conductive film of recording in TOHKEMY 2011-98563 communique, coiling in order to make to prepare transparent and electrically conductive film is good, lamination slip hard conating on the face of the opposition side of tin-doped indium oxide layer, the thickness of this slip hard conating is 1.0～10.0 μ m, the light transmission particulate that contains 0.5～30 quality %, the mean grain size of this light transmission particulate is thickness 10～60%.
But, the slip hard conating of recording in TOHKEMY 2011-98563 communique, the coiling when preparing transparent and electrically conductive film is abundant not.This be due to use mean grain size be thickness 10～60% light transmission particulate thereby the projection that forms at slip hard coating surface less.
Therefore, the object of this invention is to provide a kind of transparent and electrically conductive film and as the tint correction film of its basement membrane, this transparent and electrically conductive film can suppress to see through the painted of light, total light transmittance is high, and coiling is excellent.
For the technological means of dealing with problems
The first invention relates to a kind of tint correction film, and it is to start lamination the first hard conating, the first color tone correcting layer and the second color tone correcting layer successively from the surface of transparent base film; At rear side lamination second hard conating of transparent base film, this tint correction film has the pliability that can reel, it is characterized by, and the refractive index of the light that described the first hard conating is 400nm for wavelength is 1.51～1.61, and thickness is 1.3～3.5 μ m; Described the first color tone correcting layer consists of metal oxide microparticle and active energy ray curable resin, and the refractive index of the light that is 400nm for wavelength is 1.63～1.86, and thickness is 25～90nm; Described the second color tone correcting layer consists of silicon dioxide microparticle and active energy ray curable resin, and the refractive index of the light that is 400nm for wavelength is 1.33～1.53, and thickness is 10～55nm; The bonding agent that described the second hard conating contains 80～98wt%, the Photoepolymerizationinitiater initiater of 1～10wt%, the mean grain size of 0.01～19wt% is the organic fine particles of 0.8～5.5 μ m, the refractive index of the light that is 400nm with respect to wavelength is 1.51～1.61, thickness is 1.3～3.5 μ m, and the mean grain size of organic fine particles be the second hard conating thickness 61～350%, described bonding agent and Photoepolymerizationinitiater initiater, mean grain size are that the organic fine particles sum of 0.8～5.5 μ m is 99～100wt%.
Being characterized as of the second invention, in the tint correction film of the first invention, the active energy ray curable resin that the bonding agent of the second hard conating contains 29～75wt% and the silicon dioxide microparticle of 12～60wt%, simultaneously, with respect to described the second hard conating, described active energy ray curable resin and described silicon dioxide microparticle sum are 80～98wt%.
The 3rd invention relates to the transparent and electrically conductive film that a kind of described the second color tone correcting layer upper strata at the first invention and the second tint correction film of inventing is pressed with tin-doped indium oxide layer, it is characterized by, the refractive index of the light that described tin-doped indium oxide layer is 400nm for wavelength is 1.85～2.35, and thickness is 5～50nm.
Invention effect
Tint correction film about the present invention's the first invention, by composition and the thickness of the specific layer of suitable setting (the first color tone correcting layer, the second color tone correcting layer, the second hard conating), can maintain good coiling, can bring into play and reduce the effect that sees through optical colour simultaneously.In addition, the thickness in the present invention refers to physics thickness, rather than blooming.
Tint correction film about the present invention's the second invention, bonding agent is set, making active energy ray curable resin-phase is 29～75wt% for the second hard conating, and silicon dioxide granule is 12～60wt% with respect to the second hard conating, thereby can make coiling property better.
About the transparent and electrically conductive film of the present invention's the 3rd invention, by refractive index and the thickness of suitable setting the first hard conating, the first color tone correcting layer, the second color tone correcting layer and tin-doped indium oxide layer, can suppress to see through the painted of light.
And, in the transparent and electrically conductive film of the 3rd invention, by using the refractive index that wavelength is 400nm to design each layer, make to suppress to see through the coloring effect maximization of light.
Embodiment
(tint correction film)
The tint correction film of present embodiment is that the one side from transparent base film starts successively lamination the first hard conating, the first color tone correcting layer, the second color tone correcting layer and forms, at another side lamination second hard conating of transparent base film.The tint correction film of present embodiment, by composition and the thickness of the specific layer of suitable setting (the first color tone correcting layer, the second color tone correcting layer, the second hard conating), can maintain good coiling, meanwhile, can bring into play and reduce the effect that sees through optical colour.
And the transparent and electrically conductive film of present embodiment, is lamination tin-doped indium oxide layer on the second color tone correcting layer.And transparent and electrically conductive film, by using the refractive index of the light that wavelength is 400nm to design each layer, makes to suppress to see through the maximum effect of optical colour.
The reason of the refractive index of the light that to use in the present embodiment with respect to wavelength be 400nm is described here.Refractive index has wavelength dispersibility, has refractive index become large tendency in short wavelength region.Usually, about adjusting each layer of refractive index, although mostly use the value of the D line (light that wavelength is 589nm) of sodium, in contain the layer of metal oxide microparticle as the color tone correcting layer of present embodiment and tin-doped indium oxide layer, refractive index is subject to the impact of wavelength dispersion to become large.When suppressing yellow colour developing, the transmitance that control wavelength is 400nm is extremely important, but in the situation that adjust each layer of refractive index by the refractive index that wavelength is 589nm, can not fully adjust the transmitance that wavelength is 400nm, therefore cannot obtain reducing fully the effect of yellow colour developing.
Below, the textural element of this tint correction film is described successively.
(transparent base film)
Transparent base film consists of polyester film, for example, can use polyethylene terephthalate (PET) resin.The thickness of transparent base film is generally 25～400 μ m left and right, is preferably 25～188 μ m left and right.In addition, transparent base film is in situation about being formed by PET resin, and the refractive index of the light that transparent base film is 400nm with respect to wavelength is 1.72.
(the first hard conating)
In order to improve skin hardness, on transparent base film, be provided with the first hard conating.
As the material of the first hard conating, for existing known, be not particularly limited.For example, can enumerate by ultraviolet ray (UV) and solidify the solidfied material that the first hard conating obtains with masking liquid, this first hard conating masking liquid is that tetraethoxysilane isoreactivity silicon compound and active energy ray curable mixed with resin are formed.As active energy ray curable resin, such as enumerating simple function (methyl) acrylate, multifunctional (methyl) acrylate etc.Wherein, from taking into account the viewpoint of productive capacity and hardness, consider, preferably contain pencil hardness (evaluation method: JIS-K5600-5-4) be the solidfied material of the composition of active energy ray curable resin more than H.As the composition that contains such active energy ray curable resin, can use the composition that has for example mixed two or more well-known active energy ray curable resins, the commercially available composition as ultraviolet hardening hard coat material, or in addition, in not damaging the scope of effect of the present invention, use the composition that has further added other compositions.In addition, in this manual, " (methyl) acrylate " refers to acrylate and methacrylate.
The refractive index of the light that to adjust the first hard conating be 400nm with respect to wavelength, is 1.51～1.61.In the situation of refractive index less than 1.51, because the refringence between transparent base film and the first hard conating becomes large, produce interference fringe, therefore not preferred.Refractive index is greater than in 1.61 situation, for refractive index is increased, need to add more high-index material to the first hard conating.Now, can produce absorption and the scattering of light of the light causing because of high-index material in the first hard conating, the first hard conating occurs painted, and total light transmittance reduction, therefore not preferred.In addition, the thickness after the first hard conating dry solidification is 1.3～3.5 μ m.In the thinner situation of Film Thickness Ratio 1.3 μ m, due to the not enough H of pencil hardness, therefore not preferred.In the thicker situation of Film Thickness Ratio 3.5 μ m, when causing curling grow because of cure shrinkage, thickening unnecessarily, productive capacity and operability reduce, therefore not preferred.
(the second hard conating)
In order to improve skin hardness, make coiling property good, in the rear side of transparent base film, be provided with the second hard conating.
The second hard conating be for example, by utilizing active energy beam (ultraviolet ray, electron beam) that the second hard conating is solidified with masking liquid solidfied material form, this second hard conating masking liquid is that the organic fine particles that is 0.8～5.5 μ m by bonding agent and Photoepolymerizationinitiater initiater, mean grain size mixes.Second hard conating of take after solidifying is 100wt%, and bonding agent and Photoepolymerizationinitiater initiater, mean grain size are that the organic fine particles sum of 0.8～5.5 μ m is 99～100wt%, can in the scope below 1wt%, add other compositions as required.As other compositions, the levelling agent that can be mixed, the low-index material of adjusting refractive index or high-index material etc.In addition, from the viewpoint of coating, consider, at the second hard conating with conventionally containing diluting solvent in masking liquid.
Second hard conating of take after solidifying is 100wt%, and the addition of bonding agent is 80～98wt%.The in the situation that of the not enough 80wt% of bonding agent, skin hardness is not enough, therefore not preferred.On the other hand, bonding agent is than in the many situations of 98wt%, and the quantitative change of organic fine particles is few, cannot form projection on the surface of the second hard conating, result, and coiling is insufficient.
Bonding agent preferably has active energy ray curable resin and silicon dioxide microparticle (aftermentioned).For example, bonding agent preferably contains the active energy ray curable resin of 29～75wt% and the silicon dioxide microparticle of 12～60wt%, and with respect to the second hard conating, active energy ray curable resin and described silicon dioxide microparticle sum are 80～98wt%.Here in the situation of the not enough 29wt% of active energy ray curable resin, be difficult to the second hard conating to be maintained membranaceous, therefore not preferred.In addition, when active energy ray curable resin is used alone as to bonding agent, if active energy ray curable resin is more than 98wt%, coiling property is insufficient, therefore not preferred.
The active energy ray curable resin using as bonding agent, the refractive index of its light that is 400nm with respect to wavelength is preferably 1.4～1.7.As active energy ray curable resin, for example, can enumerate simple function (methyl) acrylate, multifunctional (methyl) acrylate etc.
Silicon dioxide microparticle is 0～60wt% with respect to the addition of bonding agent, is preferably 12～60wt%.And, in the less situation of the addition of silicon dioxide microparticle, thering is the tendency that the skin hardness of the second hard conating dies down, silicon dioxide microparticle, than in the more situation of 60wt%, has the tendency of the second hard conating albefaction, therefore not preferred.
In addition, the mean grain size of silicon dioxide microparticle is preferably below 0.1 μ m.The mean grain size of silicon dioxide microparticle, than in the larger situation of 0.1 μ m, produces scattering of light in the second hard conating, and mist degree (Haze) value uprises, and has the tendency of albefaction, therefore not preferred.In addition, in this manual " mean grain size of silicon dioxide microparticle " refer to use particle size distribution analyzer (large mound electronics (strain) is manufactured, PAR-III), the value of utilizing dynamic light scattering determination mean grain size to try to achieve.Haze value can be measured according to JIS-K-7105 or JIS-K-7136 in addition.
The silicon dioxide microparticle using as bonding agent, can be used solid silicon dioxide microparticle or hollow silica particles.The refractive index of solid silicon dioxide microparticle is 1.4～1.5, and the refractive index of hollow silica particles is 1.2～1.4.
In the large situation of the refractive index ratio 1.5 of silicon dioxide microparticle, produce the scattering of light that the refringence by active energy beam hardening resin and silicon dioxide microparticle causes, there is the tendency of the optical property reduction of the second hard conating.In the little situation of the refractive index ratio 1.2 of silicon dioxide microparticle, can be observed the weakened of hollow silica particles, the tendency of mar resistance variation, but the addition of the silicon dioxide microparticle using due to the second hard conating is few, the impact that mar resistance is worsened is little.Therefore, even if the refractive index of the silicon dioxide microparticle using in the second hard conating is below 1.2, also no problem at technical elements.
The Photoepolymerizationinitiater initiater using in the second hard conating is for ultraviolet ray (UV), to solidify the second hard conating to use with masking liquid.As the addition of Photoepolymerizationinitiater initiater,, with respect to the second hard conating 100wt% after solidifying, be preferably 1～10wt%.If Photoepolymerizationinitiater initiater is fewer than 1wt%, the second hard conating is curing insufficient.On the other hand, in the situation that Photoepolymerizationinitiater initiater is more than 10wt%, the Photoepolymerizationinitiater initiater in the second hard conating unnecessarily increases, and the optical property of the second hard conating has the tendency of reduction.As such Photoepolymerizationinitiater initiater, such as using 1-hydroxyl-cyclohexyl-phenyl-one, 2-methyl isophthalic acid-[4-(first sulphur) phenyl]-2-morpholino propane-1-ketone etc.
Second hard conating of take after solidifying is 100wt%, and the mean grain size of using in the second hard conating is that the organic fine particles of 0.8～5.5 μ m contains 0.01～19wt%, and, the mean grain size of organic fine particles be the second hard conating thickness 61～350%.
Mean grain size be the organic fine particles of 0.8～5.5 μ m in the situation that of not enough 0.01wt%, coiling is insufficient.On the other hand, organic fine particles is than in the many situations of 19wt%, and the second hard conating generation albefaction, therefore not preferred.
In 61% situation of the thickness of mean grain size less than second hard conating of organic fine particles, organic fine particles is imbedded in the second hard conating, and result can not form projection on the surface of the second hard conating, and it is insufficient that coiling becomes.On the other hand, the mean grain size of organic fine particles is than 350% also in large situation of the thickness of the second hard conating, and the second hard conating produces albefaction, therefore not preferred.And the mean grain size of organic fine particles is more preferably 100%～340% of the second hard conating thickness.
As such organic fine particles, such as by the formation such as polymkeric substance as described below, described polymkeric substance is the polymkeric substance being obtained by least one monomer polymerization being selected from vinyl chloride, (methyl) acrylate monomer, styrene and ethene.In addition, in this instructions, " mean grain size of organic fine particles " refers to and uses particle size distribution analyzer (day machine dress (strain) manufacture, micro-tracking (micro track) MT3200II), the value of utilizing laser diffraction, scattering method mean grain size to try to achieve.
Two hard conatings of the tint correction film of present embodiment, the thickness of the first hard conating and the second hard conating and refractive index both can be mutually identical, also can be mutually different.
(the first color tone correcting layer)
The first color tone correcting layer is to utilize active energy beam (for example ultraviolet ray, electron beam) to make the first color tone correcting layer solidify with masking liquid the solidfied material obtaining to form, and this first color tone correcting layer masking liquid is that metal oxide microparticle and active energy ray curable mixed with resin are formed.As metal oxide microparticle, preferential oxidation titanium and zirconia.The refractive index of the light that titanium dioxide and zirconia are 400nm with respect to wavelength, because preparation method's difference is different, but is preferably 1.9～3.0.In addition, the active energy ray curable resin using as bonding agent, the refractive index of the light that is 400nm with respect to wavelength is preferably 1.4～1.7.As active energy ray curable resin, for example, can enumerate simple function (methyl) acrylate, multifunctional (methyl) acrylate etc.
By suitable selection metal oxide microparticle and active energy ray curable resin, form the first color tone correcting layer, the refractive index that makes its light that is 400nm with respect to wavelength is 1.63～1.86.Further, the thickness after the first color tone correcting layer dry solidification need to be 25～90nm.In the situation of the refractive index less than 1.63 of the first color tone correcting layer, the value that sees through look b* in the L*a*b colour system of JIS Z8729 regulation can become greatly, so that obviously identify the yellow colour developing that sees through look of transparent and electrically conductive film.In addition, in the large situation of the refractive index ratio 1.86 of the first color tone correcting layer, it is large that the ratio of the metal oxide microparticle in the first color tone correcting layer becomes, and haze value will rise, so total light transmittance reduces.The thickness of the first color tone correcting layer is outside above-mentioned scope time, and it is large that the value of b* becomes, so that obviously identify the yellow colour developing that sees through look painted of transparent and electrically conductive film.
(the second color tone correcting layer)
The second color tone correcting layer is to utilize active energy beam (for example ultraviolet ray, electron beam) to make the second color tone correcting layer solidify with masking liquid the solidfied material obtaining to form, and this second color tone correcting layer masking liquid is that silicon dioxide microparticle and active energy ray curable mixed with resin are formed.As silicon dioxide microparticle, preferred cataloid or hollow silica particles.The refractive index of the light that cataloid and hollow silica particles are 400nm with respect to wavelength, because preparation method's difference is different, but is preferably 1.25～1.50.In addition, the active energy ray curable resin using as bonding agent, the refractive index of the light that is 400nm with respect to wavelength is preferably 1.4～1.7.As active energy ray curable resin, for example, can enumerate simple function (methyl) acrylate, multifunctional (methyl) acrylate etc.
By suitable selection silicon dioxide microparticle and active energy ray curable resin, form the second color tone correcting layer, the refractive index that makes its light that is 400nm with respect to wavelength is 1.33～1.53.Further, the thickness after the second color tone correcting layer dry solidification is 10～55nm.In the situation of the refractive index less than 1.33 of the second color tone correcting layer, because the ratio change of silicon dioxide microparticle in the second color tone correcting layer is large, haze value rises, so total light transmittance reduces.In addition, in the large situation of the refractive index ratio 1.53 of the second color tone correcting layer, the value that sees through look b* in the L*a*b colour system of JIS Z8729 regulation will become greatly, so that obviously identify the yellow that sees through look of transparent and electrically conductive film, develops the color.The thickness of the second color tone correcting layer is outside above-mentioned scope time, and it is large that the value of b* becomes, so that obviously identify the yellow colour developing that sees through look painted of transparent and electrically conductive film.
(formation of the first hard conating, the second hard conating, the first color tone correcting layer and the second color tone correcting layer)
The first hard conating is on transparent base film, to be coated with the first hard conating with after masking liquid, by irradiating active energy beam, solidify to form.The second hard conating is on the face of the first hard conating opposition side with transparent substrate layer, and coating the second hard conating, with after masking liquid, solidify to form by irradiating active energy beam.
On the other hand, the first color tone correcting layer is to be coated with the first color tone correcting layer with after masking liquid on the first hard conating forming, and by irradiating active energy beam, solidify to form.Further, the second color tone correcting layer is to be coated with the second color tone correcting layer with after masking liquid on the first color tone correcting layer forming, and by irradiating active energy beam, solidify to form.The first masking liquid for hard conating, the second masking liquid for hard conating, the first masking liquid for color tone correcting layer, the second color tone correcting layer are not particularly limited with the coating process of masking liquid, can adopt any known method, such as rolling method, method of spin coating, dip coating, spraying rubbing method, excellent rubbing method, scraper for coating method, die coating method, spraying process, intaglio plate rubbing method etc.In addition, the kind of active energy beam is not particularly limited, but considers from viewpoints such as conveniences, preferably uses ultraviolet ray.In addition,, in order to improve the attaching of each hard conating, can on transparent base film surface, implement the pre-treatments such as Corona discharge Treatment in advance.
(transparent and electrically conductive film)
Transparent and electrically conductive film has tin-doped indium oxide layer on the second color tone correcting layer of tint correction film.That is, the structure of transparent and electrically conductive film is from lamination tin-doped indium oxide layer, the second color tone correcting layer, the first color tone correcting layer, the first hard conating, transparent base film, the second hard conating successively above.
The b* of the painted Lab colour system that can stipulate with JIS Z8729 that sees through light of transparent and electrically conductive film evaluates, and is preferably-2≤b*≤2 more preferably-1≤b*≤1.The in the situation that of b* > 2, owing to observing on nesa coating, be coloured to yellow, therefore not preferred.On the other hand, the in the situation that of b* <-2, due to can observe nesa coating be coloured to light blue, therefore not preferred.
The total light transmittance of transparent and electrically conductive film is preferably more than 88%.In the situation of total light transmittance less than 88%, visibility variation, therefore not preferred.In addition, haze value less than 1%.Above in the situation that, there is albefaction 1% in haze value, visibility variation, therefore not preferred.
(tin-doped indium oxide layer (ITO layer))
On the second color tone correcting layer, the tin-doped indium oxide layer of lamination (ITO layer) is transparency conducting layer, and the refractive index of the light that is 400nm with respect to wavelength is 1.85～2.35, and thickness is 5～50nm.If refractive index is not within the scope of this, owing to there is no suitable effect with the optical interference of the first color tone correcting layer and the second tint correction interlayer, presenting through look of transparent and electrically conductive film is painted, and total light transmittance also reduces.In addition, the refractive index of ITO layer is preferably large than the refractive index of the second color tone correcting layer.In the thinner situation of the Film Thickness Ratio 5nm of ITO, ITO layer is difficult to form uniform thickness, can not get stable resistance, therefore not preferred.In addition, in the thicker situation of the Film Thickness Ratio 50nm of ITO layer, by the absorption grow of the light of ITO layer self, reduce the effect that sees through chromatic colorant and alleviate, meanwhile, there is the tendency that total light transmittance diminishes, therefore not preferred.
(formation of tin-doped indium oxide layer)
The film-forming method of tin-doped indium oxide layer is not particularly limited, for example, can adopt vapour deposition method, sputtering method, ion plating, CVD (chemical vapor deposition) method.Wherein, from the viewpoint of key-course thickness, consider, particularly preferably vapour deposition method and sputtering method.In addition, form after tin-doped indium oxide layer, as required, in the scope of 100 ℃～200 ℃, implement annealing in process, can crystallization.Particularly, if crystallization at high temperature, the refractive index of tin-doped indium oxide layer demonstrates the tendency diminishing.Therefore, the refractive index of tin-doped indium oxide layer can be adjusted by controlling the temperature and time of annealing in process.
Embodiment
Below, enumerate embodiment and comparative example described embodiment is further specifically described, but the present invention is not limited in the scope of these embodiment.In addition, the refractive index in each example, see through look, total light transmittance is measured with method as follows.
(refractive index (layer outside ITO layer))
(1) on the PET film that is 1.72 in the refractive index of the light that is 400nm with respect to wavelength (trade name " A4100 ", Toyo Boseki K.K manufacture), use dipping to lift coating machine (Physicochemical apparatus Co., Ltd. of China fir mountain unit manufactures), be coated with respectively masking liquid for each layer, adjust bed thickness, making the thickness after its dry solidification is 100～500nm left and right.
(2) after dry, under nitrogen atmosphere, utilize ultraviolet illuminating instrument device (Iwasaki Electric Co., Ltd.'s manufacture), use 120W high-pressure mercury-vapor lamp, irradiate 400mJ ultraviolet ray, be cured.PET film inner face after solidifying is coarse with sand papering, all coats blackwash, uses reflection beam splitting film thickness gauge (manufacture of " FE-3000 ", Otsuka Electronics Co., Ltd.), measures its reflectance spectrum.
(3), according to the reflectivity being read by reflectance spectrum, obtain the constant of the n Cauchy's of unit (n-Cauchy) as follows wavelength dispersion formula (formula 1), refractive index when calculating optical wavelength is 400nm.
N (λ)=a/ λ
4+ b/ λ
2+ c (formula 1)
(N: refractive index, λ: wavelength, a, b, c: wavelength dispersion constant)
(refractive index (ITO layer))
(1) on the PET film that is 1.72 in the refractive index of the light that is 400nm with respect to wavelength (trade name " A4100 ", Toyo Boseki K.K manufacture), use the ITO target of indium: tin=10:1 to carry out sputter, the tin-doped indium oxide layer of the transparency conducting layer that formation is 20nm as actual thickness (ITO layer), each condition with following embodiment and comparative example is implemented annealing, makes transparent and electrically conductive film.
(2) coarse with sand papering at above-mentioned transparent and electrically conductive film inner face, all coat blackwash, use reflection beam splitting film thickness gauge (manufacture of " FE-3000 ", Otsuka Electronics Co., Ltd.), measure its reflectance spectrum.
(3) according to the reflectivity that read by reflectance spectrum, the refractive index while utilizing above-mentioned formula (1) to obtain optical wavelength to be 400nm.
In addition, the refractive index of each layer of recording in each table (aftermentioned), is the refractive index of being obtained for measuring the sample of refractive index by above-mentioned.
(seeing through look)
Use colour difference meter (" SQ-2000 ", Japanese electricity Se Industrial Co., Ltd manufacture), that measures transparent and electrically conductive film sees through look b*.This b* is the value of the L*a*b colour system of JIS Z8729 regulation.
(total light transmittance haze value)
Use mist degree instrument (" NDH2000 ", Japanese electricity Se Industrial Co., Ltd manufacture), measure total light transmittance (%) and the haze value of transparent and electrically conductive film.
(coiling)
Transparent and electrically conductive film is reeled with 6 inches of cores, by visual, observe, with metewand as follows, the coiling of film is evaluated.
◎: the concavo-convex variations such as pleat and indenture of not reeling completely.
Zero: the concavo-convex variations such as pleat and indenture of substantially not reeling.
*: the concavo-convex variation such as coiling pleat and indenture is large.
(preparation of the first masking liquid for hard conating (HC1-1))
The isobutyl alcohol that mixes the dipentaerythritol acrylate of 96 mass parts, the Photoepolymerizationinitiater initiater of 4 mass parts (trade name: prepared by IRGACURE184 Ciba (Ciba Specialty Chemicals) (strain)) and 100 mass parts, preparation the first masking liquid for hard conating (HC-1).Using the refractive index of the first hard conating of the first masking liquid for hard conating (HC-1) formation is 1.55.
(preparation of masking liquid for the second hard conating)
As the second hard conating masking liquid, use following raw material, the composition of being recorded with following table 1 and table 2 mixes each raw material, and preparation is masking liquid HC2-1～HC2-18, HC ' 2-1～HC ' 2-6 for the second hard conating.In addition, the numerical value in table 1 and table 2 is wt%.Measure and use the second hard conating masking liquid HC2-1～HC2-18 making, the refractive index of formed the second hard conating of HC ' 2-1～HC ' 2-6.Its result is illustrated in table 1 and table 2.
As active energy ray curable resin, use dipentaerythritol acrylate.In addition as Photoepolymerizationinitiater initiater, the IRGACURE184 (I-184) that uses Ciba (strain) to prepare.In addition, it as mean grain size, is the organic fine particles of 0.8～5.5 μ m, 1.5 μ m) or combine and grind MX-500 (mean grain size: 5.0 μ m) prepared by chemistry (strain) use to combine the MX-80H3wT that grinds chemistry (strain) and prepare (mean grain size: 0.8 μ m), and combine the MX-150 that grinds chemistry (strain) and prepare (mean grain size:.Ratio mixed adhesive, Photoepolymerizationinitiater initiater and organic fine particles and solvent with weight ratio 1:1.As solvent, use methyl isobutyl ketone.
(table 2)
(preparation of masking liquid for the first color tone correcting layer)
As the first color tone correcting layer masking liquid, use following raw material, the composition of being recorded with following table 3 mixes each raw material, and preparation is masking liquid C1-1～C1-4 for the first color tone correcting layer.In addition, the numerical value in table 3 is wt%.Measure the refractive index of using the first hard conating making to use the formed color tone correcting layer of masking liquid C1-1～C1-4.Its result is illustrated in table 3.
As metal oxide microparticle, use zirconia particle dispersion liquid (uncommon love changes into (strain) and prepares ZRMEK25%-F47) or titanium oxide microparticle dispersion liquid (uncommon love changes into (strain) and prepares RTTMIBK15WT%-N24).In addition, as active energy ray curable resin, use 6 functional polyurethanes acrylate (Japanese synthetic chemical industry (strain) is prepared purple light UV-7600B).Ratio mixed-metal oxides particulate and active energy ray curable resin, Photoepolymerizationinitiater initiater and solvent with weight ratio 100:5:1000.As Photoepolymerizationinitiater initiater, the IRGACURE184 (I-184) that uses Ciba (strain) to prepare.As solvent, use methyl isobutyl ketone in addition.
(table 3)
(preparation of masking liquid for the second color tone correcting layer)
Preparation as the second color tone correcting layer with masking liquid, is used starting material below, and the composition of being recorded with following table 4 mixes each raw material, and preparation is masking liquid C2-1～C2-5 for the second color tone correcting layer.In addition, the numerical value in table 4 is wt%.Measure the refractive index of using the second color tone correcting layer making to use the formed color tone correcting layer of masking liquid C2-1～C2-5.Its result is illustrated in table 4.
As silicon dioxide microparticle, use and to wave catalyst day and change into acryloyl group prepared by (strain) and modify hollow silica particles suru-ria (ス ル ー リ ア) XBA-ST for preparing of NAU or daily output chemistry (strain).In addition,, as metal oxide microparticle, use zirconia particle dispersion liquid (uncommon love changes into ZRMEK25%-F47 prepared by (strain)).In addition, as active energy ray curable resin, the DPHA that uses Japanese chemical drug (strain) to prepare.
Ratio hybrid fine particles composition (silicon dioxide microparticle or metal oxide microparticle) and active energy ray curable resin, Photoepolymerizationinitiater initiater and solvent with weight ratio 100:5:4000.As Photoepolymerizationinitiater initiater, the IRGACURE907 (I-907) that uses Ciba (strain) to prepare.And, as solvent, use isopropyl alcohol.
(table 4)
(embodiment 1-1)
At thickness, be on a face of PET film of 125 μ m, use excellent coating machine to be coated with the first masking liquid for hard conating (HC1-1), utilize 120W high-pressure mercury light irradiation 400mJ ultraviolet ray, it is solidified, form the first hard conating.Then, on the another side of PET film, use excellent coating machine to be coated with the second masking liquid for hard conating (HC2-1), utilize 120W high-pressure mercury light irradiation 400mJ ultraviolet ray, it is solidified, form the second hard conating.
On above-mentioned the first hard conating, use excellent coating machine to be coated with the first masking liquid for color tone correcting layer (C1-1), utilize 120W high-pressure mercury light irradiation 400mJ ultraviolet ray, it is solidified, form the first color tone correcting layer.On above-mentioned the first color tone correcting layer, use excellent coating machine to be coated with the second masking liquid for color tone correcting layer (C2-1), utilize 120W high-pressure mercury light irradiation 400mJ ultraviolet ray, it is solidified, form the second color tone correcting layer, make tint correction film (S1-1) (with reference to following table 5).
(embodiment 1-2～embodiment 1-16, embodiment 2-1～embodiment 2-10)
Except making the first hard conating, the first color tone correcting layer, the second color tone correcting layer, the second hard conating, be following table 5 and table 6 material and thickness recorded, identical with embodiment 1-1, make tint correction film (S1-2～S1-16, S2-1～S2-10).
(embodiment 3-1)
On the second color tone correcting layer of above-mentioned tint correction film (S1-1), use the ITO target of indium: tin=10:1 to carry out sputter, thereby the tin-doped indium oxide layer (ITO layer) that formation thickness is 20nm is implemented 30 minutes annealing in process at 150 ℃, makes transparent and electrically conductive film.To resulting transparent and electrically conductive film, with preceding method, measure coiling, see through look b*, total light transmittance and haze value.Result is illustrated in following table 7.
(embodiment 3-2～embodiment 3-18, embodiment 4-1～embodiment 4-10)
Except making thickness that tin-doped indium oxide layer (ITO layer) records for table 7 and table 8, identical with embodiment 2-1, make transparent and electrically conductive film.
(comparative example 1-1～comparative example 1-13, comparative example 2-1～comparative example 2-3)
Except making the first hard conating, the first color tone correcting layer, the second color tone correcting layer, the second hard conating, be following table 9 and table 10 material and thickness recorded, identical with embodiment 1-1, make tint correction film (S ' 1-1～S ' 1-13, S ' 2-1～S ' 2-3).
(table 10)
(comparative example 3-1～comparative example 3-14, comparative example 4-1～comparative example 4-3)
Except making thickness that tin-doped indium oxide layer (ITO layer) records for table 11 and table 12, identical with embodiment 3-1, make transparent and electrically conductive film.
(table 12)
(result and investigation)
In embodiment 3-1～embodiment 3-18, embodiment 4-1～embodiment 4-10, because the refractive index and film thickness of the first hard conating and each color tone correcting layer, tin-doped indium oxide layer is set in scope given to this invention, therefore the value that sees through look b* is little, can fully suppress the painted of transparent and electrically conductive film, further, can realize excellent total light transmittance.In addition, in embodiment 3-1～embodiment 3-18, embodiment 4-1～embodiment 4-10, because the composition of the second hard conating and thickness are set in scope given to this invention, therefore can realize excellent coiling.
On the other hand, in comparative example 3-1～3-7, comparative example 3-14, due to any one of the refractive index of the first hard conating, each color tone correcting layer, tin-doped indium oxide layer and thickness is set in outside scope given to this invention, therefore its result is large through the value of look b*, transparent and electrically conductive film occurs painted, or haze value is high, total light transmittance is low.
In comparative example 3-8～3-13, comparative example 4-1～4-3, due to any one of the composition of the second hard conating and thickness is set in outside scope given to this invention, so its result coiling is poor, or haze value is high, and total light transmittance is low.
The tint correction film of present embodiment and transparent and electrically conductive film are not limited in above-mentioned embodiment, also can obtain other various embodiments.
Claims (3)
1. a tint correction film, it is to start lamination the first hard conating, the first color tone correcting layer, the second color tone correcting layer successively from the surface of transparent base film, and at rear side lamination second hard conating of transparent base film, this tint correction film has the pliability that can reel, it is characterized in that
The refractive index of the light that described the first hard conating is 400nm with respect to wavelength is 1.51～1.61, and thickness is 1.3～3.5 μ m;
Described the first color tone correcting layer consists of metal oxide microparticle and active energy ray curable resin, and the refractive index of its light that is 400nm with respect to wavelength is 1.63～1.86, and thickness is 25～90nm;
Described the second color tone correcting layer consists of silicon dioxide microparticle and active energy ray curable resin, and the refractive index of its light that is 400nm with respect to wavelength is 1.33～1.53, and thickness is 10～55nm;
The bonding agent that described the second hard conating contains 80～98wt%, the Photoepolymerizationinitiater initiater of 1～10wt%, the mean grain size of 0.01～19wt% are the organic fine particles of 0.8～5.5 μ m, the refractive index of the light that is 400nm with respect to wavelength is 1.51～1.61, thickness is 1.3～3.5 μ m, and, the mean grain size of organic fine particles be the second hard conating thickness 61～350%;
Described bonding agent and Photoepolymerizationinitiater initiater, mean grain size are that the organic fine particles sum of 0.8～5.5 μ m is 99～100wt%.
2. tint correction film as claimed in claim 1, it is characterized in that, the active energy ray curable resin that the bonding agent of described the second hard conating contains 29～75wt% and the silicon dioxide microparticle of 12～60wt%, simultaneously, with respect to described the second hard conating, described active energy ray curable resin and described silicon dioxide microparticle sum are 80～98wt%.
3. a transparent and electrically conductive film, it is the transparent and electrically conductive film of lamination tin-doped indium oxide layer in described second Hue layer of claim 1 or tint correction film claimed in claim 2, it is characterized in that,
The refractive index of the light that described tin-doped indium oxide layer is 400nm with respect to wavelength is 1.85～2.35, and thickness is 5～50nm.
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| JP2012037460 | 2012-02-23 | ||
| JP2012-037460 | 2012-02-23 | ||
| PCT/JP2013/053361 WO2013125408A1 (en) | 2012-02-23 | 2013-02-13 | Color tone correction film and transparent conductive film using same |
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| JP (1) | JP5423926B1 (en) |
| KR (1) | KR101761463B1 (en) |
| CN (1) | CN103959105B (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105247389A (en) * | 2013-05-27 | 2016-01-13 | 日东电工株式会社 | Hard coat film and hard coat film roll |
| CN106218067A (en) * | 2016-08-31 | 2016-12-14 | 惠州市摩码菱丽光电材料有限公司 | A kind of colour correction film and preparation method thereof |
| CN109451735A (en) * | 2017-07-10 | 2019-03-08 | 东山薄膜株式会社 | The hard coating film and transparent and electrically conductive film with optical adjustment layer of transparent and electrically conductive film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6263980B2 (en) * | 2013-11-19 | 2018-01-24 | 大日本印刷株式会社 | Transparent conductive film forming substrate, transparent conductive substrate and touch panel |
| JP6405902B2 (en) * | 2014-11-05 | 2018-10-17 | 日油株式会社 | Color tone correction film and transparent conductive film using the same |
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| JP5408075B2 (en) * | 2009-10-06 | 2014-02-05 | 日油株式会社 | Transparent conductive film |
| TWI406091B (en) * | 2010-06-17 | 2013-08-21 | Univ Nat Kaohsiung Applied Sci | The curable composition and the preparation method of the article having the transparent protective layer using the composition |
| JP5803062B2 (en) * | 2010-07-12 | 2015-11-04 | Tdk株式会社 | Transparent conductor and touch panel using the same |
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- 2013-02-13 CN CN201380004004.0A patent/CN103959105B/en not_active Expired - Fee Related
- 2013-02-13 JP JP2013510148A patent/JP5423926B1/en not_active Expired - Fee Related
- 2013-02-13 WO PCT/JP2013/053361 patent/WO2013125408A1/en active Application Filing
- 2013-02-13 KR KR1020147021402A patent/KR101761463B1/en active IP Right Grant
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| JP2000301648A (en) * | 1999-04-19 | 2000-10-31 | Teijin Ltd | Transparent conductive laminate and transparent tablet |
| CN2534590Y (en) * | 2002-02-01 | 2003-02-05 | 杨树梅 | Winding transparent energy-saving film |
| US20070212498A1 (en) * | 2006-02-24 | 2007-09-13 | Fujifilm Corporation | Optical film, antireflection film, polarizing plate, display apparatus and method for manufacturing optical film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105247389A (en) * | 2013-05-27 | 2016-01-13 | 日东电工株式会社 | Hard coat film and hard coat film roll |
| CN106218067A (en) * | 2016-08-31 | 2016-12-14 | 惠州市摩码菱丽光电材料有限公司 | A kind of colour correction film and preparation method thereof |
| CN109451735A (en) * | 2017-07-10 | 2019-03-08 | 东山薄膜株式会社 | The hard coating film and transparent and electrically conductive film with optical adjustment layer of transparent and electrically conductive film |
| CN109451735B (en) * | 2017-07-10 | 2022-05-10 | 东山薄膜株式会社 | Hard coat film with optical adjustment layer for transparent conductive film, and transparent conductive film |
Also Published As
| Publication number | Publication date |
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| KR101761463B1 (en) | 2017-07-25 |
| CN103959105B (en) | 2015-07-01 |
| JPWO2013125408A1 (en) | 2015-07-30 |
| TWI559338B (en) | 2016-11-21 |
| JP5423926B1 (en) | 2014-02-19 |
| KR20140125772A (en) | 2014-10-29 |
| TW201335956A (en) | 2013-09-01 |
| WO2013125408A1 (en) | 2013-08-29 |
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