CN103765249B - The manufacture method of antireflection film, antireflection film, polarization plates and image display device - Google Patents

The manufacture method of antireflection film, antireflection film, polarization plates and image display device Download PDF

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Publication number
CN103765249B
CN103765249B CN201280023924.2A CN201280023924A CN103765249B CN 103765249 B CN103765249 B CN 103765249B CN 201280023924 A CN201280023924 A CN 201280023924A CN 103765249 B CN103765249 B CN 103765249B
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low
antireflection film
index layer
stain
layer
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CN103765249A (en
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筱原诚司
林真理子
秋山健太郎
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

According to the present invention, there is provided easily to manufacture and there is excellent preventing reflection characteristic, there is excellent mar resistance and soil resistance, and suppress so far never by the manufacture method of the antireflection film of the generation of slight albefaction bothered about, antireflection film and the polarization plates and the image display device that use this film.The invention provides the manufacture method of antireflection film, it comprises operation (1) successively and is coated with the low-index layer formation composition at least containing fluorochemicals, particulate and adhesive resin over the transparent substrate thus the operation forming film; Operation (2) makes this film be separated into the operation of low-refraction phase and antifouling phase; And operation (3) heats this low-refraction phase and this antifouling phase, or irradiate ionizing ray mutually to this low-refraction phase and this are antifouling, form the operation of the stain-proofing layer of whole of low-index layer and this low-index layer coating, this antireflection film has transparent base, low-index layer and stain-proofing layer at least successively, fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from this stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25, and the average surface roughness of this stain-proofing layer (Ra ') be below 10nm.

Description

The manufacture method of antireflection film, antireflection film, polarization plates and image display device
Technical field
The present invention relates to the manufacture method of antireflection film, antireflection film, polarization plates and image display device.
Background technology
In the past, on the surface of the displays such as liquid crystal display (LCD), plasma display device (PDP), cathode tube display device (CRT), antireflection film is set in order to give high surface hardness or prevent the preventing reflection characteristic that reflects caused by the light that irradiates from the external light source such as incandescent lamp, fluorescent light.Usually, antireflection film is the film with the formation being laminated with hard conating and low-index layer over the transparent substrate, and this low-index layer, in order to contribute to antireflection, is preferably more low-refraction.In addition, as the method being used for realizing antiradar reflectivity, such as higher for the refractive indexes such as middle index layer, high refractive index layer is stacked as film layer by layer by known elder generation on above-mentioned hard conating, then forms the method for above-mentioned low-index layer.In addition in such as patent documentation 1, disclose the antireflection film containing specific particulate in refractive index inhibition layer.
On the other hand, as the performance required by antireflection film, the mar resistance of above-mentioned display surface can be enumerated, or not easily made dirty because of fingerprint or sebum, marking pen etc., even and if adhere to these dirts also easy wiping, i.e. soil resistance.As the method for giving antireflection film soil resistance, there is the method (such as patent documentation 1) using the anti fouling agents such as fluorine-containing anti fouling agent.But, patent documentation 1 is in order to suppress the hydraulic performance decline etc. resulted from containing the gonorrhoea of antifoulant composition, and improve the mutual solubility with each composition in said composition, weight-average molecular weight namely must be used to be less than the low-molecular-weight fluorine-containing anti fouling agent of about 5000, the soil resistance of gained cannot be claimed to be abundant.
As the method for giving soil resistance, it is also proposed in the stain-proofing layer being arranged at its surface, by using the fluorochemicals with perfluoroalkyl etc., making with the relation of element silicon, carbon and fluorine element, there is the method (such as patent documentation 2) of the fluorine atom of specified quantitative.Knownly to use at patent documentation 2, there is the fluorochemicals of perfluoroalkyl etc., though be the material of soil resistance excellence, but with other material forming stain-proofing layer, the mutual solubility of such as adhesive resin is poor, thus, when the resin combination comprising this fluorochemicals for coating is to form stain-proofing layer, is sometimes difficult to form stable stain-proofing layer, or also has the situation that albefaction problem occurs.
From this point, owing to being obviously deteriorated with the mutual solubility of other composition in patent documentation 2, there is the harmful effects such as depression or inequality, albefaction to not cause coated face, by with the relation of element silicon, carbon and fluorine element, the fluorine atom of specified quantitative is existed, and obtains certain mutual solubility, thus form stain-proofing layer, wish the generation (patent documentation 2, paragraph [0039]) forming stable stain-proofing layer or suppress albefaction.
In recent years with the high performance of display described above, antireflection film also pursues high performance, and especially the requirement of whitening improves.In the past, if spoken parts in an opera, referring to can the albefaction of the degree of the reduction film transparency that identification is such at a glance, and what pursue is exactly reduce this albefaction.But in recent years, except albefaction in the past, also require to suppress so far never by the slight albefaction bothered about, this slight albefaction is thinking to have in the film of high transparent at first blush, the albefaction of the degree that art personnel inadequate ability order is known, by patent documentation 2, there is coated surface and be not uniformity and the situation etc. that has some deformation, have cannot be fully completely corresponding situation.
In addition, as the method for giving film soil resistance, propose on the hyaline membrane base material arranging anti-reflection layer, evaporation contains the silane coupling agent of holo-fluorine polyester to form the method (such as patent documentation 3) of stain-proofing layer.This method described in patent documentation 3, because have the fluorochemicals of perfluoroalkyl etc. described above, poor with the intermiscibility usually forming other material of stain-proofing layer, be difficult to carry out being coated with to form stain-proofing layer as this resin combination comprising fluorochemicals, thus attempt adopting the method not using other material with regard to the cambial so-called evaporation of energy, it is desirable to comprise the stain-proofing layer masking of this fluorochemicals.But, layer is formed owing to adopting evaporation, therefore just other materials such as adhesive resin cannot be used, due to the layer intensity of stain-proofing layer or be deteriorated with the adaptation of hyaline membrane base material, therefore wiping several times will cause stain-proofing layer to be peeled off and soil resistance obviously declines from film, also because evaporation must carry out under the high temperature of hundreds of degree, thus hyaline membrane base material is had to shrink because of heating, or in the activated deterioration test carried out for the goods before circulation, there is the problems such as decomposition in the base material itself being subject to fire damage because of high temperature deposition.
Stain-proofing layer generally makes its thickness reach nm rating scale, make it thin in the extreme, thus except the soil resistance of excellence, also must suppress the generation of slight albefaction, in order to meet these conditions simultaneously, can thinking except using the material each other with intermiscibility as the composition forming stain-proofing layer, also must research and develop further and could realize.
[patent documentation 1] Japanese Unexamined Patent Publication 2010-152311 publication
The open text of No. 2008/38714th, [patent documentation 2] International Publication
[patent documentation 3] Japanese Unexamined Patent Publication 2001-188102 publication
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the section representing antireflection film of the present invention.
Fig. 2 is the schematic diagram of the section representing antireflection film of the present invention.
Fig. 3 is the schematic diagram of the section representing antireflection film of the present invention.
Fig. 4 is that the surface of the antireflection film of embodiment 1 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Fig. 5 is that the surface of the antireflection film of embodiment 2 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Fig. 6 is that the surface of the antireflection film of embodiment 3 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Fig. 7 is that the surface of the antireflection film of embodiment 4 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Fig. 8 is that the surface of the antireflection film of embodiment 5 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Fig. 9 is that the surface of the antireflection film of comparative example 1 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Figure 10 is that the surface of the antireflection film of comparative example 2 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Figure 11 is that the surface of the antireflection film of comparative example 3 gained is by the X rays topographs of atomic force microscope gained and phase place picture.
Description of reference numerals
1. antireflection film
2. transparent base
3. low-index layer
4. hard conating
5. index layer in
6. high refractive index layer
7. high refractive index layer in
8. stain-proofing layer
Summary of the invention
The technical matters that invention will solve
The object of the invention is to, there is provided in this condition, easily can manufacture and there is excellent preventing reflection characteristic, there is excellent mar resistance and soil resistance, and suppress so far never by the manufacture method of the antireflection film of the generation of slight albefaction bothered about, antireflection film and the polarization plates and the image display device that use this film.
Technological means
The present inventor etc. attentively study to achieve these goals and repeatedly, when found that the method formation stain-proofing layer according to patent documentation 2, sometimes on its surface, form the uneven existence of solidfied material of the composition of stain-proofing layer, or the circular or oval uneven existence in hole, thus the island structure that the lower floor that can see base material etc. exposes, the generation of this structure produces obstruction to forming stable stain-proofing layer, and then causes occurring so far never by the slight albefaction bothered about.Namely, method disclosed in patent documentation 2, exist by making the fluorine atom of specified quantitative, obtain certain intermiscibility, though improve the easiness forming stain-proofing layer thus, under the situation of more high performance pursuing antireflection film, whether stain-proofing layer is formed uniformity, whether generate island structure, slight albefaction occurs, also have the leeway of research further.
Therefore, the discoveries such as the present inventor, and improve intermiscibility unlike seeking in the past, but specially by using the low-index layer formation composition of the specific fluorochemicals containing the fluorine atom comprising more intermiscibility difference, and the method making it be separated after adopting coating said composition, to form layer by the mode of said composition film surface integral, thus the generation that can obtain island structure described above obtains the little and low-index layer of uniformity of the average surface roughness of suppression, thus solve above-mentioned problem.
In addition, although the fluorochemicals soil resistance excellence that fluorine atom content is many, because intermiscibility is poor, never considered to contain in resin combination to use in the past, but this fluorochemicals can be used in the present invention, and extremely excellent soil resistance can be obtained.The present invention completes based on this opinion just.
That is, the invention provides:
[1] a kind of manufacture method of antireflection film, it comprises following operation (1) ~ (3) successively, this antireflection film has transparent base, low-index layer and stain-proofing layer at least successively, fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from this stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25, the average surface roughness of this stain-proofing layer (Ra ') be below 10nm
Operation (1) is coated with the low-index layer formation composition at least containing fluorochemicals, particulate and adhesive resin over the transparent substrate, forms the operation of film,
Operation (2) makes this film be separated into the operation of low-refraction phase and antifouling phase,
Operation (3) heats this low-refraction phase and this antifouling phase, or irradiates ionizing ray mutually to this low-refraction phase and this are antifouling, forms the operation of the stain-proofing layer of whole of low-index layer and this low-index layer coating;
[2] antireflection film, it is by manufactured by the manufacture method of the antireflection film described in above-mentioned [1];
[3] polarization plates, it has antireflection film at least one side of polarizing coating, the antireflection film of this antireflection film described in above-mentioned [2]; And
[4] image display device, it has antireflection film or polarization plates in the outmost surface of display, and this polarization plates is the polarization plates at least one side of polarizing coating with antireflection film, the antireflection film of this antireflection film described in above-mentioned [2].
Invention effect
Easily can obtain that there is excellent preventing reflection characteristic according to the present invention, there is mar resistance and the soil resistance of excellence, and suppress so far never by the antireflection film of the generation of slight albefaction bothered about, and the polarization plates and the image display device that use this antireflection film can be obtained.
Embodiment
[manufacture method of antireflection film]
The manufacture method of antireflection film of the present invention is the method manufacturing antireflection film, comprising operation (1) is successively coated with at least containing fluorochemicals over the transparent substrate, the low-index layer formation composition of particulate and adhesive resin, thus form the operation of film, operation (2) makes this film be separated into the operation of low-refraction phase and antifouling phase, and operation (3) heats this low-refraction phase and this antifouling phase, or irradiate ionizing ray mutually to this low-refraction phase and this are antifouling, form the operation of the stain-proofing layer of whole of low-index layer and this low-index layer coating, described antireflection film has transparent base at least successively, low-index layer, and stain-proofing layer, fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from this stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25, the average surface roughness of this stain-proofing layer (Ra ') be below 10nm.
The low-refraction phase formed in operation (2) and antifouling phase, it is the phase formed in the film of coating low-index layer formation composition, adhesive resin in low-index layer formation composition is uncured state, in addition, the solvent preferably comprised in the composition, is in vaporized state under the degree that completes of being separated.On the other hand, these phases by through operation (3), form that adhesive resin in this layer becomes solid state, solvent then evaporates and more than half non-existent low-index layer and stain-proofing layer.Therefore, in the present invention, the state be present in film is called low-refraction phase, antifouling phase, by being called low-index layer, stain-proofing layer through operation (3).In addition, in the present invention, uncured state refers to that low-index layer formation composition has the state of the mobility of physics, gets final product viscometric state, solid state refers to that low-index layer formation composition does not have the state of the mobility of physics, namely cannot viscometric state.
Below each operation is explained.
(operation (1))
Operation (1) is coated with the low-index layer formation composition at least containing fluorochemicals, particulate and adhesive resin over the transparent substrate, thus form the film formation process of film.
In the present invention, film formation process preferably by preparation transparent base, prepare low-index layer formation composition in addition, this transparent base is coated with this low-index layer formation composition carries out.
(preparation of low-index layer formation composition)
Low-index layer formation composition is by fluorochemicals described later, particulate, adhesive resin and the homogeneous mixing such as the fluoropolymer preferably used or various adjuvants, and makes it be dissolved in solvent and prepare as required.
This low-refraction formation composition, if consider throughput rate, is preferably dissolved in the aqueous of solvent.The viscosity of aqueous low-index layer formation composition, as long as the viscosity that can be formed film by coating method described later on the surface of transparent base, there is no particular restriction.
(formation of film)
The formation of film is on the surface of transparent base, in the mode making the thickness after solidification become aftermentioned set thickness, by such as above-mentioned and preparation low-index layer formation composition, by the known manner of intaglio plate coating, rod coating, the coating of roller coat cloth, trans roller coat, comma, mould coating etc., be coated with carry out preferably by intaglio plate coating, mould coating.
Below, each composition forming transparent base and low-index layer formation composition is described.
(transparent base)
Transparent base used in the present invention, as long as the transparency used usually used as the base material of antireflection film is then not particularly limited, but preferably according to purposes, suitably can select plastic foil, plastic tab etc.
As this plastic foil or plastic tab, the various material comprising synthetic resin can be enumerated.As synthetic resin, the straight-chain of polyvinyl resin, ethylene-alpha-olefin multipolymer, acrylic resin, polymethylpentene resin, polybutene resin, ethylene-propylene copolymer, propene-1-butene copolymer, olefin series thermoplastic elastomer or their potpourri etc. or the polyolefin resin of ring-type can be enumerated; The vibrin of pet resin (PET), polybutylene terephthalate resin, PEN-m-phthalic acid copolymer resins, Polyester thermoplastic elastomer etc.; The acrylic resins such as poly-(methyl) methacrylate resin, poly-(methyl) ethyl acrylate resin, poly-(methyl) butyl acrylate resin; With the polyamide that nylon 6 or nylon66 fiber etc. are representative; The cellulose-based resins such as triacetyl cellulose resin (TAC), diacetyl cellulose, acetate butyrate cellulose, cellophane; The cyclic polyolefin resin that norborene, bicyclopentadiene, tetracyclododecen etc. can obtain from cycloolefin; Polystyrene resin; Polycarbonate resin; Polyarylate resin; Or polyimide resin etc.
As transparent base, can by among above-mentioned plastic foil, plastic tab, use with independent form or select two or more to make potpourri and use, from the view point of physical strength, be preferably pet resin or acrylic resin, from optically anisotropic viewpoint, be preferably triacetyl cellulose resin or cyclopolyolefin.
For the thickness of transparent base, there is no particular restriction, is generally about 5 ~ 1000 μm, if consider permanance or operability etc., is preferably 15 ~ 80 μm, is more preferably 20 ~ 60 μm.
(low-index layer formation composition)
The low-index layer formation composition used in the present invention is the resin combination containing fluorochemicals, particulate and adhesive resin.Below each composition is explained.
(fluorochemicals)
In order to form stain-proofing layer at antireflection film of the present invention, low-index layer formation composition comprises fluorochemicals.As fluorochemicals used in the present invention, preferably there is the compound of reactive group and holo-fluorine polyester, wherein, preferably can enumerate containing there is the silane unit of reactive group and there is the compound of silane unit of holo-fluorine polyester.In the present invention, by fluorochemicals, there is reactive group, can be combined by other composition easily in composition, thus can form firmer layer, as a result, the not only thin but also layer of excellent scratch resistance can be obtained.In addition, the excellent scratch resistance of antireflection film outmost surface in the present invention, also refers to the layer of outmost surface and the excellent adhesion of its lower floor simultaneously.Namely, with make the fluorochemicals in low-index layer formation composition low-refraction phase and antifouling mutually in for this antifouling mutually in the mode of more exist, in aftermentioned operation (3) during solidification, the reactive group be contained in this fluorochemicals of each phase reacts each other, can obtain adaptation very excellent between low-index layer and stain-proofing layer thus.And then, by the reactive group of this fluorochemicals and the reaction of the reactive group of adhesive resin or the solidification of adhesive resin itself, thus improve the adaptation of stain-proofing layer further, and hardness improves, and comprehensively becomes the very excellent layer of mar resistance.
In addition, comprise the compound of silane unit described above, due to low-refraction mutually in contained particulate there is affinity, antifouling phase time is formed on the surface of low-refraction phase, the wellability of whole throughout this surface can be given, even if the state of almost evaporating from mutually because being in solvent in addition also can keep wellability, so obtain the stain-proofing layer of uniformity from the view point of the whole face on this surface, it is important.And then, because this compound is very soft, improve sliding, so the layer of excellent scratch resistance can be obtained.And, wellability can be obtained sustainedly and stably because having affinity, therefore depression occurring during solvent evaporation or generates island structure to be inhibited, thus also being suppressed by the generation of these slight albefactions.And then, by being used in the fluorochemicals in same a part with silane unit and perfluor ether, being separated of silane unit and PFPE can being suppressed, easily can obtain the surface of uniformity more.At this, silane unit is the unit represented by following general formula (1).
In formula (1), X represents singly-bound or oxygen atom, R 1and R 2represent the organic group of monovalence, and R 1and R 2in at least one be the monovalent organic group comprising reactive group or holo-fluorine polyester.Fluorochemicals used in the present invention can be such as have R 1for comprising silane unit and the R of the monovalent organic group of reactive group 1for comprising the fluorochemicals of the silane unit of the monovalent organic group of holo-fluorine polyester, can also be that there is R 1for comprising the monovalent organic group of reactive group and R 2for comprising the fluorochemicals of the silane unit of the monovalent organic group of holo-fluorine polyester.In addition, in multiple silane unit, R 1, R 2and X is independently, as long as namely fluorochemicals of the present invention at least containing having the silane unit of reactive group and having the silane unit of holo-fluorine polyester, then also can be the compound with multiple silane unit.
In the present invention, these silane unit preferably have the unit of siloxane backbone.Namely being preferably X in above-mentioned formula (1) is oxygen atom.Have siloxane backbone by fluorochemicals, the affinity of the particulate that itself and low-index layer described above comprise becomes good, thus can obtain uniformity and have the stain-proofing layer of excellent stain, not easily occurring slight albefaction.
The weight-average molecular weight of fluorochemicals (what measure with GPC method is scaled poly weight-average molecular weight) is preferably more than 5000, is more preferably 5000 ~ 100000, and more preferably 5000 ~ 50000.As long as the weight-average molecular weight of fluorochemicals just can obtain excellent soil resistance more than 5000, as long as good solubility in organic solvent just can be obtained below 100000, thus be easy to the surface obtaining uniformity.
As reactive group; preferably can enumerate reactive group or epoxy radicals, carboxyl, amino, the hydroxyl etc. of the ethene unsaturated double-bond base with (methyl) acryloyl group, vinyl etc.; in these, preferably there is the reactive group of the ethene unsaturated double-bond base of (methyl) acryloyl group, vinyl etc.If reactive group is above-mentioned group, then can more easily be combined by other composition in low-index layer formation composition, therefore can form the layer that the adaptation of low-index layer and stain-proofing layer is as described above firmer, the not only thin but also layer of excellent scratch resistance can be obtained, thus preferably.
As holo-fluorine polyester, such as, preferably can enumerate the represented group of following general formula (2).
In formula (2), a ~ e is the integer of 0 ~ 50, can identical also can be different.A ~ d preferably makes that the weight-average molecular weight of the holo-fluorine polyester represented by formula (2) becomes integer in the scope of 200 ~ 6000, e is preferably 0 ~ 2.In addition, xa, xb, xc and xd are the integers of 1 ~ 4, can identical also can be different.When xa, xb, xc and xd are 3 and 4 ,-C xaf 2xa,-C xbf 2xb,-C xcf 2xc, and-C xdf 2xdcan be straight-chain and also can be branched.
The content of the fluorine atom in fluorochemicals is preferably 5 ~ 80 mass parts, is more preferably 10 ~ 70 mass parts, is more preferably 20 ~ 60 mass parts further.If the content of the fluorine atom in fluorochemicals is more than 5 mass parts, then can obtains excellent soil resistance, if below 80 mass parts, then can obtain good solubility in a solvent, therefore be easy to the surface obtaining uniformity.
Relative to total amount (solid constituent) 100 mass parts of the aftermentioned particulate in low-index layer formation composition and adhesive resin (use when fluorochemical monomer and fluoropolymer and also comprise these compositions), the solid component content of fluorochemicals is preferably 5 ~ 30 mass parts.In addition, although fluorochemicals, particulate and adhesive resin can obtain with commercially available product, but normally peddle with the form be contained in solvent.Now, the amount of these solid constituents removes the amount after solvent by the total amount of commercially available product.Though such as Photoepolymerizationinitiater initiater is for being contained in one of any solid constituent in composition in addition, be not counted in when calculating the content of fluorochemicals.
If the content of fluorochemicals is more than 5 mass parts, then with fluorochemicals, whole for surface can be coated to the stain-proofing layer of uniformity, therefore there will not be island structure, also slight albefaction occur.In addition, if below 30 mass parts, then can not there is coated surface unevenness, occur the coarse of concavo-convex etc. coated surface, the stain-proofing layer of uniformity can be obtained, also slight albefaction can not occur, obtain excellent mar resistance.That is, by making the content of fluorochemicals in above-mentioned scope, can obtain average surface roughness (Ra ') is the uniformity of below 10nm, level and smooth stain-proofing layer.
Examine rate from same reasons therewith, the content of fluorochemicals is more preferably 5 ~ 20 mass parts, more preferably 5 ~ 15 mass parts, further more preferably 10 mass parts as maximum level.By making maximum level be 10 mass parts, average surface roughness described later (Ra ') can be made further to be below 5nm, thus become more level and smooth surface and mar resistance is also good.
(particulate)
Low-index layer formation composition contains particulate.Particulate uses in order to namely the refractive index of lower layer improves preventing reflection characteristic.
As particulate, no matter be inorganic system, organic system any one can unrestrictedly use, from the view point of improving preventing reflection characteristic further and guaranteeing good skin hardness, from the view point of material, preferably can enumerate silicon dioxide microparticle, magnesium fluoride particulate etc., consider with the viewpoint of shape, preferably use spherical and itself there is the particulate in space.In addition, there is the situation in space, usually also can use the alumina particulate that the cured film refractive index of specific viscosity mixture resin is high.
In these, from the view point of material, if consider damp and hot permanance etc., preferably silicon dioxide microparticle.In the present invention, in order to form stain-proofing layer with whole the form being coated on low-index layer, the combination forming the material of these layers is one of important condition.Because particulate exists with the state of roughly fine and closely woven filling in whole of the surface of low-index layer, the proterties on the surface of this low-index layer has the tendency of the impact by particulate.Particulate contained in low-index layer, higher with the affinity of the material forming stain-proofing layer, stain-proofing layer more can easily be formed in the mode of whole that is coated on this low-index layer.This is because, when antifouling be separated mutually from low-refraction time, this is antifouling becomes mutually has wellability at the whole mask in the surface of low-refraction phase and can keep wellability until operation (3) completes.From this point of view, particularly preferably particulate is using the silicon dioxide microparticle of silicon dioxide as material, and fluorochemicals is silane unit, the combination namely comprising the fluorochemicals of silicon atom further for having siloxane unit.
Itself there is the particulate in space, owing to there is small space in outside or inside, fill the gases such as the air of such as refractive index 1.0, thus there is the feature that the refractive index of itself is low.As this particulate with space; the porous microparticles of inorganic system or organic system, hollow minute particle etc. can be enumerated, such as, preferably can enumerate porous polymer particulate or the Procedure of Polymerized Micro-Particles with Hollow of porous silica, hollow silica particles or use acrylic resin etc.As the particulate of inorganic system, the silicon dioxide microparticle with space prepared by the technology disclosed in employing Japanese Unexamined Patent Publication 2001-233611 publication of can enumerating is as preferred example; As the particulate of organic system, Procedure of Polymerized Micro-Particles with Hollow prepared by the technology disclosed in employing Japanese Unexamined Patent Publication 2002-80503 publication of can enumerating etc. are as preferred example.
There is silicon dioxide or the porous silica in space described above, its refractive index is about 1.20 ~ 1.44, due to the usual silicon dioxide microparticle that refractive index is about 1.45 lower than refractive index, thus from the viewpoint of the low-refraction of low-index layer be preferred.
In addition, as particulate, preferably also can enumerate based on its form, structure, state of aggregation, disperse state in film inside and can at the inner and/or surperficial particulate forming nanoporous structure at least partially.
As this particulate, above-mentioned silicon dioxide microparticle can be enumerated, or increasing specific surface area is manufactured as object and the porosity sections on filling post and surface absorb various chemical substance slow-release material, be used for porous microparticles that catalyzer fixes or the dispersion being used for the hollow minute particle for the purpose of heat-barrier material or dielectric materials or condensed matter etc.As concrete example, such as, can enumerate " NIPSIL (trade name) ", " NIPGEL (trade name) ": Japanese silica industry Co., Ltd. system; Or " COLLOIDSILICAUP series (trade name) ": Nissan Chemical Ind Ltd etc.
The mean grain size of the primary particle of particulate is preferably 5 ~ 200nm, is more preferably 5 ~ 100nm, is more preferably 10 ~ 80nm further.If the mean grain size of particulate is more than 5nm, then can obtain excellent refractive index decline effect, if below 200nm, then can not damage the transparency of low-index layer 3 and obtain the disperse state of good particulate.In addition, as long as mean grain size is in above-mentioned scope in the present invention, to be then connected to form chain also passable for particulate.At this, the mean grain size of the primary particle of particulate, that antireflection film section is utilized transmission electron microscope (TEM), carry out the observation of any three view sections, on photo, actual measurement is present in the diameter of any 20 particles (three view sections add up to 60 particles) of this section, is averaged particle diameter.
In addition, the particulate used in the present invention, is preferably surface treated particulate.As surface treatment, preferably can enumerate the surface treatment using silane coupling agent, wherein, preferably use the surface treatment with the silane coupling agent of (methyl) acryloyl group.By implementing surface treatment to particulate, improve the affinity with adhesive resin described later, the dispersion of particulate becomes even, be difficult to particulate cohesion each other occurs, therefore the transparence of the low-index layer caused due to macroparticle can be suppressed to decline, or the coating of low-index layer formation composition, the coating strength of said composition decline.In addition; when silane coupling agent has (methyl) acryloyl group, because this silane coupling agent has ionizing ray curability, easily react with adhesive resin described later; therefore, in the film of low-index layer formation composition, particulate is fixed by bonding agent resin.That is, particulate has the function as crosslinking chemical in adhesive resin.Thus, can obtain the tension effect of this film entirety, adhesive resin can retain original flexibility and directly give excellent skin hardness to low-index layer.Therefore, low-index layer is out of shape by the flexibility playing itself, thus the absorbability had external impact or restoring force, therefore, it is possible to suppress the generation of scar, become the layer of the high surface hardness with excellent mar resistance.
As the silane coupling agent preferably used in the present invention, 3-(methyl) acryloxypropyl trimethoxy silane of can illustrating, 3-(methyl) acryloxypropyl triethoxysilane, 3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl diethoxy silane, 2-(methyl) acryloxypropyl trimethoxy silane, 2-(methyl) acryloxypropyl triethoxysilane etc.
The content of particulate in low-index layer, is preferably 10 ~ 95 quality %, is more preferably 20 ~ 90 quality %, is more preferably 30 ~ 90 quality % further.At this, the content of particulate in low-index layer, it is the total solid composition with low-index layer composition, namely, on fluorochemicals, particulate and adhesive resin, the content of adding the particulate in the total amount (total amounts of all compounds beyond the solvent comprised in said composition) of the adjuvants such as arbitrarily used fluoropolymer, fluorochemical monomer or polymerization initiator is same meaning.If the content of particulate is more than 10 quality %, fully can obtain the effect using above-mentioned particulate, if less than 95%, then can reduce the average surface roughness (Ra ') of stain-proofing layer, can also fill and lead up between particulate gap each other well with resin, obtain excellent skin hardness.
In addition, to improve for the purpose of mar resistance in the present invention, the solid microspheres without space can be used simultaneously.The mean grain size of the primary particle of this solid microspheres is preferably 1 ~ 200nm, is more preferably 1 ~ 100nm, is more preferably 5 ~ 20nm further.If below 1nm is then little to the contribution improving skin hardness, if more than 200nm then can damage the transparency of low-index layer, be difficult to obtain good microparticulate state.
As long as the mar resistance of the content of solid particle required by low-index layer, refractive index etc. suitably adjust.Such as relative to the total quality of the total solid composition of low-index layer composition, be preferably 1 ~ 30 quality %, be more preferably 5 ~ 20 quality %.
From the view point of mar resistance, the transparency, it is desirable to carry out surface treatment in the same manner as the above-mentioned particulate with space.
As solid particle, the known solid particle being used in antireflection film or hard coat film etc. in the past can be used.As commercially available product, such as preferably can enumerate trade name MIBK-ST (average primary particle diameter: 12nm) and MIBK-ST-ZL (average primary particle diameter: 88nm) that Nissan Chemical Industries (strain) makes, or wave catalyst day and change into the trade name OSCAL series (average primary particle diameter: 7 ~ 100nm) etc. that industry (strain) makes.
(adhesive resin)
From the view point of film forming and film strength etc., low-index layer formation composition contains adhesive resin.As adhesive resin, preferably can enumerate by solidifying with the ionizing ray of heating or irradiation ultraviolet radiation, electron beam etc., thus make headed by above-mentioned fluorochemicals, particulate, other composition etc. added immobilized resin in the layer of low-index layer as required.In addition, in the present invention, preferably low with the intermiscibility of this fluorochemicals resin, thus above-mentioned fluorochemicals can be made to be separated efficiently, be coated to the stain-proofing layer of low-index layer completely.
More specifically, as adhesive resin, such as, preferably can enumerate heat-curing resin or the ionizing ray curable resins such as melamine series, urea system, epoxy, ketone system, diallyl phthalate system, unsaturated polyester (UP) system and phenol system.Wherein, preferred ionizing ray curable resin.
So-called ionizing ray curable resin be electromagnetic wave or charged particle intrafascicular, there is the resin of the quanta of energy that can make molecule aggregation, namely the resin solidified can be occurred by irradiation ultraviolet radiation or electron beam etc.Specifically, can from using as suitably selecting among the resin of ionizing ray curability and usual polymerizable monomer and polyreactive oligomers (or prepolymer) in the past.
As polymerizable monomer, be suitably in molecule (methyl) acrylate monomer with free-radical polymerised unsaturated group, wherein preferred multi-functional (methyl) acrylate monomer.
As multi-functional (methyl) acrylate monomer, as long as have (methyl) acrylate monomer of more than 2 ethene unsaturated links in molecule, there is no specific restriction.Specifically can preferably enumerate ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate monostearate, dicyclopentenyl two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate etc. 2 official can (methyl) acrylate; Trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester etc. 3 official can (methyl) acrylate; 4 officials such as pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate can above (methyl) acrylate; The ethylene-oxide-modified thing, caprolactone modification thing, propionic acid modifier etc. of above-mentioned multi-functional (methyl) acrylate monomer.
In these, from the view point of obtaining excellent mar resistance, preferably 3 officials can above (methyl) acrylate.These multi-functional (methyl) acrylate monomers can be used alone a kind, also can combine two or more and use.More specifically, the effect material of the objects such as soil resistance, mar resistance (adaptation), anti-slight albefaction can be obtained in the present invention aptly, be preferably trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester etc. 3 official can (methyl) acrylate; 4 officials such as pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate can above (methyl) acrylate, particularly preferably pentaerythrite three (methyl) acrylate.
In the present invention, while use above-mentioned multi-functional (methyl) acrylate monomer, in order to reduce its viscosity etc., in the scope not damaging object of the present invention, suitably also mono-functional's (methyl) acrylate monomer can be used.In addition, in order to the suitable adjustment coating by increasing viscosity and the warpage prevented due to cure shrinkage, following polyreactive oligomers or polymkeric substance can be used.
Below, as polyreactive oligomers, the oligomer with free-radical polymerised unsaturated group can be enumerated in molecule, such as the oligomer etc. of epoxy (methyl) acrylic ester, carbamate (methyl) acrylic ester, polyester (methyl) acrylic ester, polyethers (methyl) acrylic ester.
In addition, polymerizing methyl methacrylate and glycidyl methacrylate in advance in the present invention, also can be used such as to obtain multipolymer, then make the glycidyl of this multipolymer and methacrylic acid or acrylic acid carboxyl condensation and the reactive polymer obtained.This reactive polymer can obtain with commercially available product form, such as can enumerate " MACROMONOMER (trade name) ": Toagosei Co., Ltd etc. as commercially available product.
In the present invention, can preferably use uv curing resin or electronic beam curing resin as ionizing ray curable resin.
When using uv curing resin as ionizing ray curable resin, relative to this uv curing resin of 100 mass parts, preferably add the Photoepolymerizationinitiater initiater about 0.5 ~ 10 mass parts, more preferably add 1 ~ 5 mass parts.As Photoepolymerizationinitiater initiater, suitably can select from usual product in the past, be not particularly limited, such as, for the polymerizable monomer in molecule with free-radical polymerised unsaturated group or polyreactive oligomers, the Photoepolymerizationinitiater initiaters such as acetophenone system, benzophenone series, benzoin system, ketal system, anthraquinone system, curing system, thioxanthones system, thiuram system (thiram), fluorine amine system can be enumerated.These can any one independent, or combination two kinds and using.These Photoepolymerizationinitiater initiaters can commercially available product form obtain, such as, " IRGACURE184 (trade name) ", " IRGACURE907 (trade name) " " IRGACURE127 (trade name) " (being Ciba (strain) system) etc. can be enumerated.
Relative to total solid composition 100 mass parts in low-index layer formation composition, the content of adhesive resin is preferably 0.5 ~ 20 mass parts, is more preferably 1 ~ 15 mass parts.If the content of adhesive resin is in above-mentioned scope, then can obtains excellent mar resistance, fluorochemicals can be made to be separated efficiently.
(fluoropolymer)
From the view point of reduction refractive index, low-index layer formation composition used in the present invention preferably comprises fluoropolymer.As fluoropolymer, such as, preferably can enumerate (methyl) acrylic acid part and completely fluorinated alkyl, thiazolinyl, aryl ester class, wholly or in part fluorinated vinyl ethers, wholly or in part fluorinated vinyl ester class, wholly or in part fluorinated vinyl ketone etc.
In addition, as fluoropolymer, preferably also comprise the material of silicon in addition to fluorine, such as, preferably can enumerate the vinylidene fluoride copolymers containing silicone containing silicone composition in multipolymer.As the silicone composition of this situation, (gathering) dimethyl siloxane can be enumerated, (gathering) di-ethyl siloxane, (gathering) diphenyl siloxane, (gathering) methyl phenyl siloxane, alkyl-modified (gathering) dimethyl siloxane, (gathering) dimethyl siloxane containing azo group, or dimethyl silicone, phenymethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, hydrogenated methyl silicone, silicone containing silanol group, silicone containing alkoxy, silicone containing phenolic group, methacryl-modified silicone, acryl-modified silicone, amino modified silicone, carboxyl acid modified silicone, carbinol-modified silicone, epoxide modified silicone, sulfhydryl modified silicone, fluorine richness silicone, polyether modified silicone etc.Wherein preferably there is the material of dimethyl siloxane structural.
In addition, in addition to the foregoing, the compound at least with 1 isocyanate group and fluorine can also be used in molecule, with the compound at least there is 1 amino, hydroxyl, carboxyl etc. and the compound of the functional group of isocyanates radical reaction reacting gained in molecule; The fluorine-containing polyvalent alcohols such as fluorine-containing polyether glycol, fluorine-containing alkyl polyols, fluorine-containing polyester polyol, fluorine-containing 6-caprolactone modified polyalcohol, react compound of gained etc. as fluoropolymer with the compound with isocyanate group.
For fluoropolymer, its refractive index is preferably 1.37 ~ 1.45.If this refractive index is more than 1.37, then owing to can obtain good solubility in a solvent, therefore process easily.In addition, if less than 1.45, then the refractive index of the low-index layer of formation can be made to be reduced to required scope.
This fluoropolymer can obtain with commercially available product form, such as preferably can enumerate OPSTARTU2181-6, OPSTARTU2181-7, OPSTARTU2202, OPSTARJN35, OPSTARTU2224 of JSR Inc., OPTOOLAR110, OPTOOLAR100 etc. of DAIKIN industrial group.
Relative to total solid composition 100 mass parts in low-index layer formation composition, the content of fluoropolymer is preferably 1 ~ 30 mass parts, is more preferably 5 ~ 25 mass parts.If the content of fluoropolymer is in above-mentioned scope, refractive index can be reduced efficiently.
(fluorochemical monomer)
From the view point of reduction refractive index, low-index layer formation composition used in the present invention preferably comprises fluorochemical monomer.From the view point of solidifying to form low-index layer efficiently and can obtaining excellent hardness, fluorochemical monomer is preferably in 1 molecule has more than 2 reactive functional groups.As this fluorochemical monomer, preferably can enumerate the fluorochemical monomer with pentaerythrite skeleton, the fluorochemical monomer with dipentaerythritol skeleton, have trimethylolpropane skeleton fluorochemical monomer, there is the fluorochemical monomer of cyclohexyl skeleton, there is the fluorochemical monomer etc. of straight-chain skeleton.In these, preferably there is the compound of pentaerythrite skeleton.
The refractive index of fluorochemical monomer is preferably 1.35 ~ 1.48, is more preferably 1.37 ~ 1.45.If the refractive index of fluorochemical monomer is more than 1.35, then can obtain good solubility in a solvent, so process easily.If in addition less than 1.48, then the refractive index of formed low-index layer can be made to be reduced to required scope.
This fluorochemical monomer can obtain with commercially available product form, the LINC3A with pentaerythrite skeleton that such as preferably can enumerate Kyoeisha Chemical Co., Ltd., the LINC such as the LINC102A series etc. with cyclohexyl skeleton.
Relative to total solid composition 100 mass parts in low-index layer formation composition, the content of fluorochemical monomer is preferably 1 ~ 30 mass parts, is more preferably 3 ~ 20 mass parts.If the content of fluorochemical monomer is in above-mentioned scope, then effectively can reduce refractive index.
(various adjuvant)
In low-index layer formation composition used in the present invention, according to required physical property, various adjuvant can be coordinated.As adjuvant, such as, preferably can enumerate weatherability modifying agent, mar proof improving agent, polymerization inhibitor, crosslinking chemical, infrared absorbent, cementability improving agent, antioxidant, levelling agent, thixotropy conferring agents, coupling agent, plastifier, defoamer, filling agent, solvent etc.
(solvent)
In addition, as the solvent preferably used in low-index layer formation composition, be not particularly limited, but, such as preferably can enumerate the alcohols such as methyl alcohol, ethanol, isopropyl alcohol (IPA); The ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; The ester such as ethyl acetate, butyl acetate class; Halogenated hydrocarbons; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, dihydroxypropane single-ethyl ether, or their potpourri etc.In these, preferably high with fluorochemicals affinity ketone, glycol ethers, particularly preferred solvent is methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters.By being used alone or as a mixture these, the dispersiveness of each compound in composition can be maintained, and in the operation that is separated (2), being separated of low-refraction phase and antifouling phase can be completed aptly.
In addition, use the situation of the solvent beyond ketone or glycol ethers, be preferably the more than at least 50% of total solvent amount containing ketone or glycol ethers, be preferably more than 70%.Particularly when using ketone, because the coating of low-index layer formation composition improves, and not easily there is uneven drying because of the evaporation rate of solvent appropriateness after the coating of said composition, in addition, can with the evaporation of solvent, make fluorochemicals be separated efficiently, therefore easily can obtain the large area film (stain-proofing layer) of uniformity.
The amount of solvent according to can uniform dissolution, disperse each composition, the mode of concentration that can not be excessive rarefied when not condensing and be coated with during preservation after composition preparation suitably adjusts.The content of the solvent in low-index layer formation composition is preferably 50 ~ 99.5 quality %, is preferably set to 70 ~ 98 quality %.By being set to this content, dispersion stabilization can be obtained excellent especially, and be applicable to the long-term composition preserved.In addition, the solvent used in low-index layer formation composition, evaporates owing to passing through carried out drying or solidification after coating said composition, is therefore present in low-index layer hardly.
(operation (2))
Operation (2) is the operation making the film formed in above-mentioned operation (1) be separated into low-refraction phase and antifouling phase.As promoting the method that is separated, such as preferably can enumerate film is heated in atmosphere method, remain in steam or the heating means of method etc. such as in autoclave.In addition, also can not heat etc., simply place until be separated.
In the present invention, after coating low-index layer formation composition, and before making the adhesive resin solidification in said composition, in this operation by heating described above or simply place, the fluorochemicals in said composition can become easy emersion in the outmost surface side (be opposition side with transparent base) of film.Consequently in the film of low-index layer formation composition, much more relatively the content being separated into fluorochemicals show the antifouling phase of soil resistance, the low-refraction phase that less show low-refraction relative to the content of fluorochemicals, and antifoulingly heat what formed in outmost surface side mutually or irradiate ionizing ray, form stain-proofing layer in the mode of whole of coating low-index layer, excellent soil resistance can be obtained thus.Namely, when being coated with low-index layer formation composition in the present invention and forming film, two phases can be separated in this film, this film has low-refraction phase and antifouling phase, by through operation described later (3), the each self-forming low-index layer of two-phase and stain-proofing layer, and then in other words, also can say it is form the low-index layer with stain-proofing layer.
Heating described above or simple time of placing, as long as fluorochemicals emersion is in the time degree of the outmost surface side of film, be generally about 1 ~ 30 second.
In addition, by heating described above or placing merely, also can make the solvent evaporation preferably comprised in low-index layer formation composition, also can evaporate this solvent as object, dry energetically.The temperature conditions of the drying of this situation is preferably the scope of 20 ~ 120 DEG C, is more preferably 40 ~ 100 DEG C, is preferably 10 ~ 180 seconds drying time, be more preferably 15 ~ 90 seconds.The ceiling temperature of baking temperature suitably can be selected according to the material of the transparent base used.On the other hand, from making fluorochemicals fast and being positively separated in outmost surface, the viewpoint forming stain-proofing layer is set out, and lower limit temperature is suitable is chosen to be 20 DEG C.In addition from the view point of making after stable to be antifoulingly separated mutually, to form stain-proofing layer, be more preferably chosen to be more than 40 DEG C.
(operation (3))
Operation (3) is the film after heating is separated, or irradiates ionizing ray to film, makes the low-refraction phase in this film and the antifouling operation becoming low-index layer and stain-proofing layer mutually separately.At this, low-index layer is the layer because of there is particulate in this layer with preventing reflection characteristic, and stain-proofing layer is the layer because of there is fluorochemicals in this layer with soil resistance.In this instructions, conveniently, because the layer comprising less fluorochemicals comparatively speaking has more excellent preventing reflection characteristic, thus low-index layer (being low-refraction phase before heating or irradiation ionizing ray) is called, because the layer comprising more fluorochemicals comparatively speaking has more excellent soil resistance, be thus called stain-proofing layer (being antifouling phase before heating or irradiation ionizing ray).
Still irradiating ionizing ray to film heating, is that the adhesive resin comprised according to low-index layer formation composition is selected.When adopting heat-curing resin as adhesive resin, select heating process.As heating condition, the solidification temperature of used heat-curing resin can be coordinated to do suitable setting, such as, can be set to 60 ~ 100 DEG C.
In addition, when adopting ionizing ray curable resin as adhesive resin, as long as irradiate ionizing ray to film.When solidifying above-mentioned film, when using electron beam as ionizing ray, with regard to its accelerating potential, can be suitable selected according to the thickness of the resin used or layer, be usually preferably with accelerating potential about 70 ~ 300kV cured coating film.
In addition, in the irradiation of electron beam, due to accelerating potential more high-penetration ability more increase, using the situation of base material as base material of meeting deterioration because of electron beam, be that mode equal in fact selectes accelerating potential by the thickness of the penetration depth with film that make electron beam, electron beam can be suppressed the unnecessary irradiation of base material, the base material deteriorates caused by excess electrons bundle can be controlled at bottom line.
Exposure dose preferably makes the cross-linking density of the curable resin in low-index layer be saturated amount, is generally 5 ~ 300kGy (0.5 ~ 30Mrad), is more preferably and selectes in the scope of 10 ~ 50kGy (1 ~ 5Mrad).
In addition, as electron beam source, there is no particular restriction, such as, Ke Kelaofu-Wal can be used to pause the various electron-beam accelerators such as type, model De Graff type, resonance transformer type, insulating core transformer type or linear pattern, Dynamitron type, high-frequency type.
Use ultraviolet as the situation of ionizing ray, such as, use the ultraviolet etc. sent by ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc lamp, xenon arc lamp, metal halid lamp etc.The exposure of energy line source, with the cumulative exposure gauge at ultraviolet wavelength 365nm, is preferably 50 ~ 500mJ/cm 2left and right.
Hinder from the view point of the oxygen on the surface preventing low-index layer resin combination, ultraviolet irradiation is preferably in a nitrogen environment, such as, carry out under the environment of below oxygen concentration 1000ppm.In the present invention after being separated, with make low-refraction phase and antifouling mutually can stably quick-setting viewpoint, most preferably be Ultraviolet radiation.
In addition, by the solidification of operation (3), solvent almost evaporates completely, drying, exists hardly in layer.Solvent is large induced evaporation in operation (2), and remains in the solvent in layer when operation (2) completes, and can think almost to evaporate completely in operation (3).
[antireflection film]
Antireflection film of the present invention follows the manufacture method according to the invention described above to obtain, more specifically, it is characterized by and at least successively there is transparent base, low-index layer, and the stain-proofing layer of whole of this low-index layer coating, this low-index layer and this stain-proofing layer use containing fluorochemicals, the low-index layer formation composition of particulate and adhesive resin forms, fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from this stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25, the average surface roughness of this stain-proofing layer (Ra ') be below 10nm.
About antireflection film of the present invention, Fig. 1 ~ 3 are used to be described.Fig. 1 is the schematic diagram of the section representing antireflection film of the present invention, and the 2nd and 3 figure are configured to example with the preferably layer of antireflection film of the present invention, represent the schematic diagram of its section.Antireflection film 1 represented by Fig. 1 is on transparent base 2, have low-index layer 3 and stain-proofing layer 8.Antireflection film 1 represented by Fig. 2 is on transparent base 2, have hard conating 4, middle high refractive index layer 7 and low-index layer 3 successively, and the antireflection film 1 represented by Fig. 3 is on transparent base 2, have hard conating 4, middle index layer 5, high refractive index layer 6, low-index layer 3 and stain-proofing layer 8 successively.The layer of antireflection film 1 of the present invention is formed, as long as have low-index layer 3 and stain-proofing layer 8 on transparent base 2 successively, then be not particularly limited, such as, preferably can enumerate the layers such as transparent base/low-index layer/stain-proofing layer, transparent base/hard conating/low-index layer/stain-proofing layer, transparent base/hard conating/middle index layer/high index layer/low index layer/stain-proofing layer, transparent base/hard conating/high refractive index layer/middle index layer/low-index layer/stain-proofing layer, transparent base/middle high index layer/low index layer/stain-proofing layer and form.In addition, although do not illustrated, than low-index layer closer to transparent base side, also can have the functional layers such as antistatic layer described later further.
(low-index layer 3 and stain-proofing layer 8)
Low-index layer 3 and stain-proofing layer 8 are the layers of the low-index layer formation composition used containing fluorochemicals, particulate and adhesive resin.These layers are the layers formed according to the manufacture method of the antireflection film of the invention described above, namely film is formed by being coated with this low-index layer formation composition over the transparent substrate, this film is separated, as the phase of two in this film, form low-refraction phase and antifouling phase, by heating these films or irradiating ionizing ray, formed respectively as the layer of low-index layer 3 with stain-proofing layer 8.And, the content of the fluorochemicals comprised in this low-index layer 3, less than the content of the fluorochemicals comprised at this stain-proofing layer 8 comparatively speaking, in addition, the stain-proofing layer 8 that the content of fluorochemicals is relatively many is on the contrary the layers showing stronger soil resistance.
(low-index layer 3)
For low-index layer 3, its refractive index, the refractive index of the layer immediately below being arranged at is set to N, when the refractive index of air is set to 1, is N 1/2situation be most preferred, such as, when layer immediately below this low-index layer 3 is the hard conating using the ionizing ray curable resin of widely used multifunctional (methyl) acrylic acid series to be formed, if consider, the N of this hard conating is 1.49 ~ 1.53, then the refractive index being preferably lower than N 0.01 is the layer of 1.48 ~ 1.52.In addition, unreasonablely to think although refractive index is lower, if consider the balance of preventing reflection characteristic and skin hardness, be then more preferably 1.25 ~ 1.45, be more preferably 1.25 ~ 1.35 further.This refractive index easily can be controlled by the use amount etc. of the kind of particulate and content or fluorochemicals.
In addition, in order to obtain best anti-reflection effect, the thickness of low-index layer 3 and refractive index, preferably meet the relation calculated from following formula (I).
d A=mλ／(4n A)(I)
In formula (I), n arepresent the refractive index of low-index layer, m represents positive odd number, and be preferably expressed as 1 (air), λ is wavelength, is preferably the value of the scope of 480 ~ 580nm.Therefore, in the present invention, from the view point of seeking low-refraction, in above-mentioned formula (I), making m=1 and make λ be mankind when feeling 480 ~ 580nm of the most dazzling wavelength, the refractive index preferably calculated from following formula (II) and thickness.
120<n Ad A<145(II)
When refractive index is described above preferable range 1.25 ~ 1.45, thickness is preferably about 80nm ~ 120nm.But, in order to make refractive index ratio lower floor lower to obtain anti-reflection effect, about thickness also can be 120nm ~ 1 μm exceeding this scope.In the present invention, the aggregate thickness being preferably low-index layer and stain-proofing layer is within above-mentioned scope.
(stain-proofing layer 8)
Stain-proofing layer 8 is average surface roughness (Ra ') is below 10nm, with uniformity the mode of whole be coated on low-index layer 3 exist, give the layer of antireflection film soil resistance of the present invention.
This stain-proofing layer 8 is layers that average surface roughness (Ra ') is below 10nm, and is the layer of uniformity.In addition, and the average surface roughness of stain-proofing layer 8 (Ra ') be preferably 0.1 ~ 10nm, be more preferably 0.1 ~ 7nm, be more preferably mar resistance further and bring up to 0.1 the highest ~ 5nm.At this, average surface roughness (Ra ') be the center line average roughness (Ra) that JISB0601 is defined, mensuration face is applied and carried out three-D expansion value, showing as " to from reference field to the value that the absolute value of the deviation of given side is averaged ", is the numerical value that following formula improves.Such as, average surface roughness (Ra ') as long as observe surface configuration by atomic force microscope (AFM), and subsidiary parsing software (such as SPIwin etc.) can be utilized to carry out image analysis to the image of gained and obtain.
R a &prime; = 1 S o &Integral; Y B Y T &Integral; X L X R | F ( X , Y ) - Z o | dXdY
Ra ': average surface roughness (nm)
S o: suppose mensuration face be desirable smooth time area (| X r-X l| × | Y t-T b|)
F (X, Y): at the height of measuring point (X, Y)
X:X coordinate
Y:Y coordinate
X l, ~ X r: the scope measuring the X-coordinate in face
Y b~ Y t: the scope measuring the Y-coordinate in face
Z o: the average height in mensuration face
Average surface roughness due to stain-proofing layer 8 is very little and uniformity as mentioned above, has excellent mar resistance and soil resistance, also has excellent preventing reflection characteristic, is thus preferably disposed on the outmost surface of antireflection film of the present invention.
The state of the uniformity of stain-proofing layer 8, other than through this average surface roughness (Ra '), also observes by atomic force microscope (AFM) and confirms particularly.Namely, if stain-proofing layer 8 is observed with atomic force microscope (AFM), then in its X rays topographs and phase place picture, the solidfied material of low-index layer formation composition can evenly exist, or uneven in the stain-proofing layer formed by this solidfied material exist circular or oval hole, and the situation making the lower floor of low-index layer or transparent base etc. expose namely to present island structure also can not occur, reach the state formed throughout whole of antireflection film 1.
Fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25 is necessary.At this, fluorine atom/carbon atomic ratio, silicon atom/carbon atomic ratio are the values that the ratio of components of fluorine atom, carbon atom and the silicon atom that foundation is measured from the stain-proofing layer side of antireflection film by X-ray photoelectron spectroscopy (XPS) calculates.
The present invention is existed more than a certain amount of by the fluorine atom in stain-proofing layer 8, and silicon atom to exist below a certain amount of, namely by using set fluorochemicals with fixed amount, can obtain performance excellent stain and without the antireflection film of slight albefaction.In addition, due to be throughout whole and uniformity form stain-proofing layer, therefore by throughout having above-mentioned atomic ratio by entire surface, more excellent soil resistance can be obtained, reduces the generation of slight albefaction.
From this point of view, fluorine atom/carbon atomic ratio is more preferably 0.7 ~ 1.0, and silicon atom/carbon atomic ratio is more preferably 0.01 ~ 0.2.If fluorine atom/carbon atomic ratio is less than 0.6, then soil resistance can be insufficient.On the other hand, if be greater than 1.0, then in order to realize the process of the reagent that this numerical value uses, namely the process of fluorochemicals will become very difficult.In addition, if silicon atom/carbon atomic ratio is more than 0.25, then soil resistance can be insufficient, therefore, makes this ratio for being less than 0.25 in the present invention, but by scope like this, can expect because sliding improves the excellent mar resistance brought.
When confirming island structure by atomic force microscope (AFM), or at the partially observable protuberance of one, when the uneven surface of average surface roughness beyond scope given to this invention, from stain-proofing layer side by the atomic ratio that X-ray photoelectron spectroscopy (XPS) measures, not in the scope of atomic ratio described above.Namely, be coated with in the film of low-index layer formation with composition gained, be separated into the situation of low-refraction phase and antifouling phase, and then stain-proofing layer as the layer of uniformity and situation about being formed, can confirm according to determining above-mentioned atomic ratio given to this invention on low-index layer; Stain-proofing layer is the situation of the layer of uniformity, also can confirm according to the mensuration by atomic force microscope (AFM).Therefore, having average surface roughness given to this invention and atomic ratio by stain-proofing layer, is except obtaining excellent soil resistance, also can obtain mar resistance and can obtain the antireflection film that slight albefaction also do not manifest.In the present invention, according to being measured by the average surface roughness of above-mentioned atomic force microscope (AFM) (Ra ') or X rays topographs and the observation of phase place picture, and the atomic ratio to be measured by X-ray photoelectron spectroscopy (XPS), or can be whether that the evaluation method of antireflection film of the present invention uses as the antireflection film determined whether manufactured by manufacturing method according to the invention.The existence of the stain-proofing layer on low-index layer, observe although sometimes also observe by TEM section, if consider very thin layer, then it is effective for stating evaluation method more than.In addition, when forming stain-proofing layer by vapour deposition methods such as chemical vapor deposition method (CVD), physical vapor depositions (PVD), different from manufacture method of the present invention, the reactive group had not in accordance with the material of each layer due to stain-proofing layer and low-index layer and reacting, therefore adaptation is weak, so mar resistance dies down.That is, can be evaluated by mar resistance, confirm the difference of manufacture method.At this, mar resistance is evaluated as following evaluation: by applying 300g/cm to steel wool (Japanese steel wool Co., Ltd. BONSTAR#0000) 2above load at the surperficial reciprocating friction 10 times of antireflection film, the visual scar number caused on this surface.
Silicon atom in low-index layer and stain-proofing layer, with SiO 2, or C-Si-O form exist, will from SiO in the present invention 2silicon atom be called inorganic silicon atom, the silicon atom from C-Si-O is called silicone atom.Namely, in the present invention, the silicon atom in low-index layer and stain-proofing layer comprises silicone atom and inorganic silicon atom.
Inorganic silicon atom and silicone atom, because bond energy is different, thinks and can separate appearance in Si2p spectrum.Be separated by crest and resolve, the crest near 103 ~ 104eV of high bond energy side is decided to be inorganic silicon atom, and the crest near 101 ~ 102eV of low bond energy side is decided to be silicone atom.Silicon atom in above-mentioned silicon atom/carbon atomic ratio, is set to the numerical value of the total amount of inorganic silicon atom and silicone atom.
In the present invention, the silicone atom/carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from stain-proofing layer side is preferably less than 0.07, is more preferably 0.01 ~ 0.07, is more preferably 0.02 ~ 0.06 further.In addition, inorganic silicon atom/carbon atomic ratio is preferably less than 0.2, is more preferably 0.05 ~ 0.2, is more preferably 0.08 ~ 0.18 further.If silicone atom/carbon atomic ratio, inorganic silicon atom/carbon atomic ratio is in above-mentioned scope, then can obtains manifesting excellent mar resistance and soil resistance, and there is no the antireflection film of slight albefaction.
By meeting above-mentioned atomic ratio in the present invention, do not need the intermiscibility seeking to improve fluorochemicals as in the past, stain-proofing layer is formed with coating form by adopting the method that uses low-index layer formation composition to make the surface integral of low-index layer be separated, this stain-proofing layer suppresses the generation of island structure described above, becomes the little and layer of uniformity of average surface roughness.
In addition, by using the low-index layer formation composition of combination fluorochemicals and particulate and adhesive resin, not only can obtain the stain-proofing layer 8 of uniformity, as a result, can also obtain that there is excellent antireflection characteristic, there is excellent mar resistance and soil resistance, and the antireflection film be inhibited of slight albefaction.
As long as level and smooth face, the organic compound that would not occur in theory because forming stain-proofing layer and so on causes the situation of the contact angle of hexadecane more than 90 °.Therefore, contact angle and landing angle can use hexadecane as mensuration liquid, are measured by various commercially available contact angle goniometer, landing angle goniometer.
Antireflection film 1 of the present invention, its outmost surface is set to the situation of stain-proofing layer 8, hexadecane be preferably 55 ~ 90 ° relative to the contact angle on surface, be more preferably 60 ~ 90 °, and hexadecane be preferably 1 ~ 25 ° relative to the landing angle on surface, be more preferably 1 ~ 20 °, its outmost surface is uniformity, and namely stain-proofing layer 8 has level and smooth structure.The fluorochemicals comprised by stain-proofing layer 8 is coated on surface, and contact angle and landing angle are in above-mentioned scope, and on the other hand, when causing to be coated to surface forming island structure, contact angle and landing angle can beyond above-mentioned scopes uniformity.
The aggregate thickness of low-index layer 3 and stain-proofing layer 8, different according to required refractive index, but from the view point of the reflectivity reduced in visible regime, as mentioned above, be preferably about 80 ~ 120nm.In addition, 100 ~ 120nm is more preferably.
The only thickness of stain-proofing layer 8, infers in the scope of 1 ~ 3nm.Also the atom that the particulate in low-index layer comprises can be detected when being analyzed by above-mentioned X-ray photoelectron spectroscopy (XPS), if and consider with the degree of depth of the information of X-ray photoelectron spectroscopy (XPS) gained for 1 ~ 3nm, then infer in the scope of 1 ~ 3nm comparatively appropriate.
(hard conating 4)
Antireflection film 1 of the present invention, in order to improve the performance of the skin hardnesses such as the mar resistance of antireflection film 1, can have hard conating 4.At this, the hard performance being coated with the hardness referred to more than display " H " in the pencil hardness test of JIS5600-5-4:1999 defined.
Hard conating preferably makes the layer of ionizing ray curable resin crosslinking curing gained.Form the ionizing ray curable resin of hard conating 4, can among the ionizing ray curable resin for the adhesive resin above-mentioned low-index layer formation composition suitable choice for use.The Photoepolymerizationinitiater initiater used during the situation that ionizing ray curable resin is uv curing resin, also can from illustrational material above suitable choice for use.In addition, the various adjuvants that above-mentioned low-index layer formation composition uses can use too.
Thickness after hard conating 4 solidifies preferably is in the scope of 0.1 ~ 100 μm, is more preferably the scope of 0.8 ~ 20 μm, is more preferably the scope of 1 ~ 8 μm further, be particularly preferably the scope of 1.5 ~ 4 μm.As long as thickness is in above-mentioned scope, just can obtains firmly being coated with performance fully, the impact from outside is not easily broken.In addition, in the present invention hard conating 4 also can be have concurrently as following illustrated in the layer of function of index layer 5 or high refractive index layer 6, or have the layer of function of antistatic layer concurrently.
(middle index layer 5 and high refractive index layer 6)
In order to improve antireflection property, antireflection film 1 of the present invention preferably can have middle index layer 5 and high refractive index layer 6.At this, middle index layer 5 and high refractive index layer 6 are the forms as antireflection film 1, do not need to arrange middle index layer 5 and high refractive index layer 6 as described above simultaneously, also such as can arrange one deck with middle high refractive index layer 7 form as shown in Figure 2.
The refractive index of middle index layer 5, high refractive index layer 6 or middle high refractive index layer 7 (hereinafter also referred to these index layers), preferably can set arbitrarily in the scope of 1.5 ~ 2.00.That is, middle index layer 5 is that at least the above-mentioned low-index layer 3 of refractive index ratio is high, the layer that refractive index ratio high refractive index layer 6 is low, and the height of refractive index is relative value.The refractive index of middle index layer 5 and high refractive index layer 6 as above-mentioned be relative value, but in being usually preferably, the refractive index of index layer 5 is in the scope of 1.5 ~ 1.8, the refractive index of high refractive index layer 6 is in the scope of 1.6 ~ 2.0.
These index layers such as by adhesive resin, with below particle diameter 100nm and the particulate with the refractive index of specifying formed.As this concrete example (representing refractive index in bracket) with the particulate of the refractive index of specifying, ZnO (1.90), TiO can be enumerated 2(2.3 ~ 2.7), CeO 2(1.95), tin indium oxide (is called for short ITO; 1.95), the tin oxide of antimony dopant (is called for short ATO; 1.80), Y 2o 3(1.87), ZrO 2(2.0).In addition, as adhesive resin, can among above-mentioned adhesive resin suitable choice for use.
The refractive index of the cured film of the refractive index ratio adhesive resin monomer of preferred particulate is high.Refractive index due to these index layers is normally determined by the containing ratio of particulate, and therefore the addition of particulate is more, and the refractive index of index layer is higher.Therefore, by adjusting the interpolation ratio of adhesive resin and particulate, the index layer with the refractive index of specifying can be formed.As long as particulate is the particulate with electric conductivity, the index layer using this particulate to be formed will become the layer having antistatic behaviour concurrently.These index layers can be the vapor-deposited film of the titania that formed by the vapour deposition method such as chemical vapor deposition method (CVD), physical vapor deposition (PVD) or the high inorganic oxide of zirconic refractive index, or use the cured film of resin inorganic oxide particle high for the refractive index of titania and so on being scattered in the resin combination of suitable binders resin.
The thickness of these index layers is preferably the scope of 10 ~ 300nm, is more preferably the scope of 30 ~ 200nm.Above-mentioned index layer (middle index layer, high refractive index layer) can directly be arranged at transparent base 2, but preferably on transparent base 2, arranges hard conating 4, arranges between hard conating 4 and low-index layer 3.
(antistatic layer)
Obtain the attachment of anti-dust from the view point of utilizing antistatic effect or antireflection film of the present invention be used in the electric conductivity of situation or the electromagnetic shielding effect of image display device, antireflection film 1 of the present invention preferably can have antistatic layer.Antistatic layer is preferably disposed between transparent base 2 and low-index layer 3, when being provided with above-mentioned hard conating 4, middle index layer 5 or high refractive index layer 6, preferably low-index layer 3 is arranged at outmost surface, and arranges in the mode of this low-index layer 3 adjacent.
Be not particularly limited as antistatic layer, such as, preferably can enumerate the layer formed by the antistatic layer composition containing resin and antistatic agent.
Be not particularly limited as antistatic agent, such as, preferably can enumerate the cationic compounds such as quarternary ammonium salt, pyridiniujm, one ~ tertiary amine base; The anionic property compounds such as sulfonate, sulfuric acid, phosphate ester salt, phosphonate; The amphoteric compounds such as amino acid system, amidosulphuric acid ester system; The nonionic compounds such as amino alcohol system, glycerine system, polyglycol system; The organometallics of the alkoxide of tin and titanium and so on; The metal chelate compound etc. of the acetylacetonate of this organometallics and so on.Also the compound quantized by above-mentioned listed compound macromolecule can be used.
As antistatic agent, also preferably can enumerate and there is tertiary amine base, level Four ammonium or metal-chelating portion, and by polymerizable compounds such as the monomer of ionizing ray polymerization or the organometallicss of oligomer or the coupling agent with functional group and so on.As long as these antistatic agent ionic liquids.
As antistatic agent, also preferably electric conductive polymer can be enumerated.Be not particularly limited as electric conductive polymer, such as can enumerate poly-(to the phenylene) of aromatic series conjugated system, the polypyrrole of heterocycle conjugated system, polythiophene, aliphatics conjugated system polyacetylene, containing there is in the poly-phenylene vinylene (ppv) of the polyaniline of heteroatoms conjugated system, mixed type conjugated system, molecule the multichain type conjugated system of the conjugated system of multiple conjugated chain, making the high molecular conductive composite body etc. of aforementioned conjugated polymer chain and saturated macromolecular grafted or block copolymerization.
As antistatic agent, also can preferably enumerate conductive metal oxide particulate.Be not particularly limited as conductive metal oxide particulate, such as, can enumerate ZnO (refractive index 1.90, the value in following bracket all represents refractive index), Sb 2o 2(1.71), SnO 2(1.997), CeO 2(1.95), tin indium oxide (is called for short ITO; 1.95), In 2o 3(2.00), Al 2o 3(1.63), the tin oxide of antimony dopant (is called for short ATO; 2.0), the zinc paste of adulterated al (is called for short AZO; 2.0) etc.
As the content of the antistatic agent in antistatic layer composition, while fully can enjoying the effect containing above-mentioned antistatic agent, preferably do not hinder suitable in the scope of the effect of above-mentioned optical laminate gained manufactured by the present invention cooperation.
Resin in antistatic layer, namely be not particularly limited as being used for the resin of antistatic layer composition, such as can enumerate with the resin-phase described in above-mentioned hard conating with the potpourri of the ionizing radiation curable resin of the resin by ultraviolet or electronic beam curing, ionizing radiation curable resin and solvent-dry type resin or thermohardening type resin etc.
Antistatic layer can be formed as follows: on above-mentioned transmitance base material etc., be coated with the antistatic layer composition that each material of above-mentioned use is prepared from and the film formed, for film, carry out drying as required, be solidified to form by ionizing radiation exposure or heating etc.
[polarization plates]
Polarization plates of the present invention has antireflection film at least one side of polarizing coating, this antireflection film is the antireflection film of the manufacture method gained according to the invention described above, namely, it is characterized by and at least successively there is transparent base, low-index layer, and the stain-proofing layer of whole of this low-index layer coating, this low-index layer and this stain-proofing layer use containing fluorochemicals, the low-index layer formation composition of particulate and adhesive resin forms, fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from this stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25, the average surface roughness of this stain-proofing layer (Ra ') be below 10nm.By being set to such formation, polarization plates of the present invention becomes the element with anti-reflective function of physical strength, excellent in light-resistance, also significantly can cut down cost, makes display device lightening.
Usual polarization plates can arrange diaphragm on the two sides of polarizing coating, however polarization plates of the present invention be its at least one side the polarization plates of antireflection film of the present invention is set.In the present invention, antireflection film of the present invention can be set at the one side of polarizing coating or two sides.When being arranged at one side, from the view point of the angle of visibility characteristic of improvement liquid crystal display picture, preferred another side is the optical compensation films (phase retardation film) with the optical compensating layer comprising optical anisotropic layer.
Using the situation that antireflection film of the present invention uses as diaphragm, as transparent supporting mass, particularly preferably use tri acetyl cellulose membrane.Now, use the transparent supporting mass of the diaphragm of antireflection film, the preferred bond layer etc. by comprising polyvinyl alcohol (PVA) is adhered to polarizing coating as required.In addition, the opposite side being preferably this polarizing coating as mentioned above also has diaphragm, preferably has the formation of above-mentioned optical compensation films (phase retardation film).Also adhering agent layer can be had with the face of the polarizing coating opposite side of another diaphragm.By being set as such formation, polarization plates of the present invention can improve the contrast of liquid crystal indicator in bright room, angle of visibility up and down.
[image display device]
Image display device of the present invention, in the outmost surface of display, there is antireflection film or polarization plates, this polarization plates is the polarization plates at least one side of polarizing coating with antireflection film, this antireflection film is the film according to above-mentioned manufacture method gained of the present invention, namely be characterized as and at least successively there is transparent base, low-index layer, and the stain-proofing layer of whole of this low-index layer coating, this low-index layer and this stain-proofing layer use containing fluorochemicals, the low-index layer formation composition of particulate and adhesive resin forms, fluorine atom/the carbon atomic ratio measured by X-ray photoelectron spectroscopy (XPS) from this stain-proofing layer side is 0.6 ~ 1.0, and silicon atom/carbon atomic ratio is less than 0.25, the average surface roughness of this stain-proofing layer (Ra ') be below 10nm.
As display, such as, preferably can enumerate liquid crystal display (LCD), plasma display device (PDP), cathode tube display device (CRT), the inorganic and display etc. such as display of organic electroluminescence, rear projection type display, fluorescent display tube (VFD), contact panel, mobile computer, Electronic Paper.In addition, as image display device, the device possessing these displays can preferably be enumerated, such as personal computer, personal digital assistant device, game machine, digital camera, Digital Video etc.
Embodiment
Below, further describe the present invention by embodiment, but the present invention is not limited due to these embodiments.
(evaluation method)
1. minimum reflectivity (evaluation of preventing reflection characteristic)
For the antireflection film in each embodiment and comparative example gained, the black belt of the backside reflection of this film is sticked to prevent in the side that transparent base does not arrange low-index layer, from the face of low-index layer, the spectrometer (" UV-2550 (model) ": Shimadzu Seisakusho Ltd.'s (strain) makes) possessing the normal reflection determinator of 5 degree is used to measure reflectivity, using the minimum value in wavelength region may 380 ~ 780nm as minimum reflectivity.Minimum reflectivity is less, represents that the preventing reflection characteristic that antireflection film has is more excellent.
2. the evaluation of coated face
Black belt is sticked, from the face forming low-index layer, with three wavelength lamp visualizations, according to following benchmark evaluation result on the film surface of the side not forming low-index layer.
Zero: the face of low-index layer is uniformity.
Δ: the face of low-index layer and the evaluation comparison of above-mentioned zero, observes slight deformation.
×: the face of low-index layer presents slight white.
3. the mar resistance on surface and the evaluation of adaptation
For the antireflection film in each embodiment and comparative example gained, be applied with 300g/cm at steel wool (Japanese steel wool Co., Ltd. BONSTAR#0000) 2load under reciprocating friction 10 times, the result visual according to following benchmark evaluation.Scar is fewer, represents that the adaptation of mar resistance and low-index layer and stain-proofing layer is more excellent.
Zero: do not cause scar completely.
Δ: scar number is 1 ~ 5.
×: scar number is more than 6.
4. the evaluation of soil resistance
After the surface attachment fingerprint of the antireflection film of each embodiment and comparative example gained, carry out wiping, with the difficulty of visual confirmation wiping, according to following benchmark evaluation with BEMCOTM-3 (Asahi Kasei Corporation's system).
Zero: can easily wiping fingerprint.
Δ: erasable fingerprint.
×: cannot wiping fingerprint.
(2) with the state of visual confirmation when the surface of the antireflection film of each embodiment and comparative example gained is described with permanent pen, with the state after cloth wiping, according to following benchmark evaluation.
◎: ink conglobulates, wiping is easy.
Zero: ink is not stained with in surface, and lines attenuate, and wiping is easy.
×: the vestige of residual ink after wiping.
5. the mensuration of the atomic ratio based on X-ray photoelectron spectroscopy of low-index layer
By x-ray photoelectron spectroscopy (XPS), analyze the surface (stain-proofing layer) of the antireflection film of each embodiment and comparative example gained, obtain atomic ratio according to following methods, this atomic ratio is which kind of degree fluorochemicals is separated to and forms the index of stain-proofing layer.
Operative installations is XPS device (" ESCALAB220i-XL (model) ", THERMOFISHERSCIENTIFIC Inc.), use X ray output power: 10kV16mA (160W), lens: LargeAreaXL (magnetic field lens), aperture opening: F.O.V.=open, A.A.=open, mensuration region: , photoelectron acceptance angle: 90 degree (at sample method Configuration Online input lens), neutralize charged: in electronics and rifle+4 (V) 0.08 (mA), in and auxiliary metal mask use under analyze.Utilize the atom composition of the carbon atom on the antireflection film surface by this mensuration gained, nitrogen-atoms, oxygen atom, fluorine atom and silicon atom, calculate fluorine atom/carbon atomic ratio and silicon atom/carbon atomic ratio.In addition, for silicon atom, the crest based on Si2p spectrum is separated resolves, and is divided into the inorganic silicon composition (SiO detecting crest near 103 ~ 104eV 2), and near 101 ~ 102eV, detect the silicone ingredients (C-Si-O) of crest, measure atom composition, calculate inorganic silicon atom/carbon atomic ratio and silicone atom/carbon atomic ratio.
6. the evaluation (mensuration at contact angle and landing angle) of surface state
For the antireflection film of each embodiment and comparative example gained, use hexadecane as mensuration liquid, utilize analyzer (" DM-500 (model) ", consonance interface science Co., Ltd. system) to measure contact angle and landing angle respectively.Drop amount is decided to be 2 μ l.
7. the evaluation (evaluation based on the surface observation of atomic force microscope) of surface state
Utilize atomic force microscope (AFM) (" L-trace (model) ", SIINANOTECHNOLOGY Co., Ltd. system), scan vibration number with dynamic mode (DynamicForceMode): 0.4 ~ 1.0Hz, sweep limit: 3 μm, observe X rays topographs and the phase place picture on the surface of the antireflection film of each embodiment and comparative example gained.Cantilever uses " OMCL-AC160TS-C2 (model) " (KSOLYMPUS Co., Ltd. system, elastic constant: 42N/m).At this, in order to the cantilever for observing does not reduce resolution because of probe needle contamination, always use brand-new product.In addition in order to prevent the wearing and tearing deterioration when observing, carrying out reduce the condition to the load of probe as far as possible in the scope of not sacrificing resolution under, carrying out the observation in resolution 512 pixel × 256 pixel.The inclination of attached software correction data is utilized after observation.
By this surface observation, when whole face, the surface of low-index layer is separated and forms stain-proofing layer, the state of uniformity can be confirmed, on the other hand, not on surface whole face be separated formed stain-proofing layer time, can confirm that surface is that the part be separated presents island pattern with the uneven pattern of the part be not separated.At this, as long as the state of uniformity, even if namely can be described as visual also without slight albefaction, coarse without coated face, form low-index layer and stain-proofing layer well.
Zero: stain-proofing layer uniformity.
Δ: although do not have island structure at stain-proofing layer, with above-mentioned zero evaluation comparison, observe slight deformation.
×: stain-proofing layer presents island structure, can be visually observed the coarse of slight albefaction or coated face.
8. the mensuration of average surface roughness (Ra ')
Observe surface configuration by above-mentioned atomic force microscope (AFM), utilize parsing software (SPIwin) to carry out image analysis, obtain average surface roughness (Ra ').
Preparation example 1: low-index layer forms the preparation with composition 1
Mix the composition of following composition with following mass ratio, prepare low-index layer formation composition 1.
Low-index layer is formed with composition 1
Pentaerythritol triacrylate (PETA): 0.10 mass parts
Fluorochemicals * 1: 1.23 mass parts
Hollow silica particle dispersion * 2: 6.69 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.74 mass parts
Fluoropolymer * 4: 2.79 mass parts
Fluorochemical monomer * 5: 2.23 mass parts
Photoepolymerizationinitiater initiater * 6: 0.08 mass parts
Methyl isobutyl ketone: 57.03 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
* 1; " X-71-1203M (trade name) ": KCC of SHIN-ETSU HANTOTAI system; 20 quality % solution (solvents: methyl isobutyl ketone; photo-curable reactive group: (methyl) acryloyl group, containing having reactive silane unit and having the fluorochemicals of silane unit of holo-fluorine polyester).
* 2, the hollow silica particle content in dispersion liquid is 20 quality %, solvent (methyl isobutyl ketone) content is 80 quality %.In addition, the mean grain size of hollow silica particle is 60nm, is had photo-curable reactive group by surface treatment.
* 3, " MIBK-SD (trade name) ", average primary particle diameter: 12nm, solid constituent: 30 quality %, solvent: methyl isobutyl ketone, solid silicon dioxide granule has the methacryl as photo-curable reactive group by surface treatment.
* 4, " OPSTARJN35 (trade name) ", JSR Inc., 20 quality % solution (solvent: methyl isobutyl ketone).
* 5, " LINC3A (trade name) ": Kyoeisha Chemical Co., Ltd.'s system, has the fluorochemical monomer of pentaerythrite skeleton, 20 quality % solution (solvent: methyl isobutyl ketone).
* 6, " IRGACURE127 (trade name) ": Ciba (strain) is made.
Preparation example 2: hard conating forms the preparation with composition 1
Mix the composition of following composition with following mass ratio, prepare hard conating formation composition 1.
Hard conating is formed with composition 1
Urethane acrylate * 7: 15 mass parts
Isocyanuric acid EO modified triacrylate * 8: 15 mass parts
Polymerization initiator * 9: 2 mass parts
Methyl ethyl ketone: 70 mass parts
* 7, " UV1700B (trade name) ", Japanese synthetic chemistry Co., Ltd. system.
* 8, " M315 (trade name) ", Toagosei Co., Ltd's system.
* 9, " IRGACURE184 (trade name) ": Ciba (strain) is made.
Embodiment 1
On triacetyl cellulose (TAC) resin molding of thickness 80 μm, rod coating hard conating is formed with composition 1, carry out the drying of 50 DEG C, 1 minute, after desolventizing, utilize ultraviolet lamp (FUSIONUVSYSTEMSJAPAN Co., Ltd. light source H-BULB), with exposure dose 30mJ/cm 2carry out Ultraviolet radiation, thus make it solidify, obtain the hard conating of thickness about 10 μm.
Then, on the hard conating of gained, rod is coated on the low-index layer formation composition 1 prepared by preparation example 1, forms film (operation (1)); Implement the heating of 50 DEG C, 1 minute, make film be separated into low-refraction phase and antifouling phase, and except after desolventizing (operation (2)); With exposure dose 200mJ/cm 2carrying out Ultraviolet radiation makes it solidify, and forms low-index layer and stain-proofing layer (operation (3)), obtains the antireflection film with transparent base, hard conating, low-index layer and stain-proofing layer.Solidify time solvent almost evaporate completely, in addition low-index layer and stain-proofing layer thickness add up to about 100nm.In addition, when measuring atomic ratio by X-ray photoelectron spectroscopy (XPS), the atom contained by the particulate in low-index layer is also detected.If the thickness considering X-ray photoelectron spectroscopy (XPS) stain-proofing layer is 1 ~ 3nm, then infer that the thickness of the stain-proofing layer of gained is in the scope of 1 ~ 3nm.
For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.In addition, atomic force microscope (X rays topographs and phase place picture) is shown in Fig. 4.
Embodiment 2
Except being replaced with except following low-index layer formation composition 2 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Fig. 5.
Low-index layer is formed with composition 2
Pentaerythritol triacrylate (PETA): 1.32 mass parts
Fluorochemicals * 1: 1.32 mass parts
Hollow silica particle dispersion * 2: 6.61 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 61.03 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Embodiment 3
Except being replaced with except following low-index layer formation composition 3 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Fig. 6.
Low-index layer is formed with composition 3
Pentaerythritol triacrylate (PETA): 0.12 mass parts
Fluorochemicals * 1: 2.07 mass parts
Hollow silica particle dispersion * 2: 6.28 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.7 mass parts
Fluoropolymer * 4: 2.62 mass parts
Fluorochemical monomer * 5: 2.09 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 56.96 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Preparation example 3: the preparation example of high refractive index layer formation composition
Drop in mayonnaise bottle and mix Titanium Dioxide Rutile Top grade (" TTO51 (C) (trade name) ", Ishihara Sangyo Kaisha, Ltd.'s system, primary particle size: 0.01 ~ 0.03 μm): 10 mass parts, spreading agent (" DISPERBYK-163 (trade name) " containing anionic property base, BYKCHEMIEJAPAN Inc.): 2 mass parts and methyl isobutyl ketone: 48 mass parts, make potpourri.Relative to the potpourri of gained, the stirring using the zirconium oxide bead (φ 0.3mm) of about its 4 times amount to carry out with coating vibrating machine 10 hours, prepares high refractive index layer formation composition.
Preparation example 4: the preparation example of middle index layer formation composition
Except in the preparation example of above-mentioned high refractive index layer formation composition, Titanium Dioxide Rutile Top grade is replaced with the tin oxide (" SN-100P (trade name) " of antimony dopant, Ishihara Sangyo Kaisha, Ltd.'s system), make the spreading agent containing anionic property base replace with beyond " DISPERBYK-111 (trade name) " (BYKCHEMIEJAPAN Inc.), index layer formation composition in preparing in the same manner as the preparation example of high refractive index layer formation composition.
Embodiment 4
On triacetyl cellulose (TAC) resin molding of thickness 80 μm, the above-mentioned hard conating formation composition 1 of rod coating, carry out the drying of 50 DEG C, 1 minute, after desolventizing, utilize ultraviolet lamp (FUSIONUVSYSTEMSJAPAN Co., Ltd. light source H-BULB), with exposure dose 30mJ/cm 2carrying out Ultraviolet radiation makes it solidify, and obtains the hard conating of thickness about 10 μm.
On the hard conating of gained, rod is coated on the middle index layer formation composition of preparation example 4 gained, with exposure dose 200mJ/cm 2carrying out Ultraviolet radiation makes it solidify, and form the high refractive index layer that thickness is about 120nm, rod is coated on the high refractive index layer formation composition of preparation example 3 gained, with exposure dose 200mJ/cm 2carrying out Ultraviolet radiation makes it solidify, and forms the high refractive index layer that thickness is about 60nm.Then, the following low-index layer formation composition 4 of rod coating, forms film (operation (1)); Implement the heating of 50 DEG C, 1 minute, make film be separated into low-refraction phase and antifouling phase, and except after desolventizing (operation (2)); With exposure dose 200mJ/cm 2carrying out Ultraviolet radiation makes it solidify, and forms low-index layer and stain-proofing layer (operation (3)), obtains the antireflection film with transparent base, hard conating, middle index layer, high refractive index layer, low-index layer and stain-proofing layer.When solidifying, solvent almost evaporates completely, and the total of the thickness of low-index layer and stain-proofing layer is about 100nm.In addition, when measuring atomic ratio by X-ray photoelectron spectroscopy (XPS), the atom of the particulate be contained in low-index layer is also detected.If the thickness considering X-ray photoelectron spectroscopy (XPS) stain-proofing layer is 1 ~ 3nm, then infer that the thickness of the stain-proofing layer of gained is in the scope of 1 ~ 3nm.
For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Fig. 7.
Low-index layer is formed with composition 4
Pentaerythritol triacrylate (PETA): 0.32 mass parts
Fluorochemicals * 1: 0.71 mass parts
Hollow silica particle dispersion * 2: 6.42 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 1.43 mass parts
Fluoropolymer * 4: 3.21 mass parts
Fluorochemical monomer * 5: 0.54 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 58.2 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Embodiment 5
Except being replaced with except following low-index layer formation composition 5 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Fig. 8.
Low-index layer is formed with composition 5
Pentaerythritol triacrylate (PETA): 0.10 mass parts
Fluorochemicals * 10: 1.23 mass parts
Hollow silica particle dispersion * 2: 6.69 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.74 mass parts
Fluoropolymer * 4: 2.79 mass parts
Fluorochemical monomer * 5: 2.23 mass parts
Photoepolymerizationinitiater initiater * 6: 0.08 mass parts
Methyl isobutyl ketone: 57.04 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
* 10; " X-71-1205 (trade name) ": KCC of SHIN-ETSU HANTOTAI system; 20 quality % solution (solvent: the potpourri of methyl isobutyl ketone and methyl ethyl ketone; photo-curable reactive group: (methyl) acryloyl group, containing having reactive silane unit and having the fluorochemicals of silane unit of holo-fluorine polyester).
Embodiment 6
Except being replaced with except following low-index layer formation composition 6 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.
Low-index layer is formed with composition 6
Dipentaerythritol acrylate (DPHA): 1.32 mass parts
Fluorochemicals * 1: 1.32 mass parts
Hollow silica particle dispersion * 2: 6.61 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 61.03 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Embodiment 7
Except being replaced with except following low-index layer formation composition 7 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.
Low-index layer is formed with composition 7
Pentaerythritol triacrylate (PETA): 0.10 mass parts
Fluorochemicals * 1: 2.93 mass parts
Hollow silica particle dispersion * 2: 5.86 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.65 mass parts
Fluoropolymer * 4: 2.44 mass parts
Fluorochemical monomer * 5: 1.95 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 56.89 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Embodiment 8
Except being replaced with except following low-index layer formation composition 8 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.By the antireflection film for gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.
Low-index layer is formed with composition 8
Pentaerythritol triacrylate (PETA): 1.32 mass parts
Fluorochemicals * 1: 1.32 mass parts
Hollow silica particle dispersion * 2: 6.61 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 61.03 mass parts
Toluene: 29.1 mass parts
Embodiment 9
Except being replaced with except following low-index layer formation composition 9 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 1.
Low-index layer is formed with composition 9
Pentaerythritol triacrylate (PETA): 0.11 mass parts
Fluorochemicals * 11: 0.25 mass parts
Hollow silica particle dispersion * 2: 6.69 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.74 mass parts
Fluoropolymer * 12: 2.79 mass parts
Fluorochemical monomer * 5: 2.23 mass parts
Photoepolymerizationinitiater initiater * 6: 0.08 mass parts
Methyl isobutyl ketone: 58.01 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
* 11, " 5101X (trade name) ": SOLVAYSPECIALTYPOLYMERSJAPAN Co., Ltd. system, the methacrylate modified per-fluoro polyether compound of two end 4 officials energy, does not have the fluorochemicals of silane unit).
* 12, " OPSTARTU2224 (trade name) ", JSR Inc., 20 quality % solution (solvent: methyl isobutyl ketone).
Comparative example 1
Except being replaced with except following low-index layer formation composition 10 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 2.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Fig. 9.
Low-index layer is formed with composition 10
Pentaerythritol triacrylate (PETA): 0.12 mass parts
Fluorochemicals * 1: 0.52 mass parts
Hollow silica particle dispersion * 2: 7.04 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.78 mass parts
Fluoropolymer * 4: 2.93 mass parts
Fluorochemical monomer * 5: 2.35 mass parts
Photoepolymerizationinitiater initiater * 6: 0.08 mass parts
Methyl isobutyl ketone: 57.09 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Comparative example 2
Except being replaced with except following low-index layer formation composition 11 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 2.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Figure 10.
Low-index layer is formed with composition 11
Pentaerythritol triacrylate (PETA): 0.09 mass parts
Fluorochemicals * 1: 3.79 mass parts
Hollow silica particle dispersion * 2: 5.44 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 0.6 mass parts
Fluoropolymer * 4: 2.27 mass parts
Fluorochemical monomer * 5: 1.81 mass parts
Photoepolymerizationinitiater initiater * 6: 0.06 mass parts
Methyl isobutyl ketone: 56.82 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Comparative example 3
Except being replaced with except following low-index layer formation composition 12 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 2.In addition, atomic force microscope figure (X rays topographs and phase place picture) is shown in Figure 11.
Low-index layer is formed with composition 12
Pentaerythritol triacrylate (PETA): 0.32 mass parts
Hollow silica particle dispersion * 2: 6.42 mass parts
Solid silicon dioxide granule dispersion liquid * 3: 1.43 mass parts
Fluoropolymer * 4: 3.21 mass parts
Fluorochemical monomer * 5: 0.54 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 58.2 mass parts
Propylene glycol monomethyl ether: 29.1 mass parts
Comparative example 4
Except being replaced with except following low-index layer formation composition 13 by the low-index layer formation composition 1 in embodiment 1, obtain antireflection film similarly to Example 1.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 2.
Low-index layer is formed with composition 13
Pentaerythritol triacrylate (PETA): 2.64 mass parts
Fluorochemicals * 1: 1.32 mass parts
Photoepolymerizationinitiater initiater * 6: 0.07 mass parts
Methyl isobutyl ketone: 95.42 mass parts
Comparative example 5
Be the solution of solid component concentration 3 quality % by the fluorochemicals that uses in embodiment 1 with a two benzotrifluorides dilution, prepare as anti-soil film vapor deposition source.
At width: 500mm, thickness: 80 μm, on triacetyl cellulose (TAC) resin molding of length: 500m, intaglio plate coating hard conating is formed with composition 1, intaglio plate is coated with following low-index layer formation composition 13, carry out the drying of 70 DEG C, 1 minute, except desolventizing, then with exposure dose 200mJ/cm 2carrying out Ultraviolet radiation makes it solidify, and the hard conating of formation thickness about 10 μm and thickness are about the low-index layer of 100nm, obtain the duplexer with transparent base/hard conating/low-index layer.
Then, in coiling type evaporation coating device, arrange above-mentioned anti-soil film vapor deposition source and duplexer, vacuum exhaust is to 1e -4after below Torr, start to batch this duplexer with the running speed of 5m/ minute, with the heating fluorescent tube of noncontact heated type, this anti-soil film vapor deposition source is evaporated, obtain the antireflection film forming anti-soil film in the low-index layer side of this duplexer.For the antireflection film of gained, the result evaluated according to above-mentioned evaluation method is shown in table 2.
Table 1
* 1, be the amount (mass parts) of the fluorochemicals of total amount 100 mass parts (solid constituent) relative to adhesive resin (use when fluorochemical monomer and fluoropolymer and also comprise these materials) and particulate.Here, solid constituent does not comprise polymerization initiator.
Table 2
* 1, be the amount (mass parts) of the fluorochemicals relative to the adhesive resin (use when fluorochemical monomer and fluoropolymer and also comprise these compositions) of 100 mass parts (solid constituent) and the total amount of particulate.At this, solid constituent does not comprise polymerization initiator.
The antireflection film of embodiment 1 ~ 5 gained, is excellence in whole evaluations, having excellent preventing reflection characteristic, having excellent mar resistance and soil resistance and without albefaction, film from the known surface for having uniformity of result at contact angle and landing angle.In addition, for embodiment 1 ~ 5, according to the observations of average surface roughness or atomic force microscope, also for having the film on the surface of uniformity, can confirm stain-proofing layer be with coating low-index layer on the mode of whole, uniformity ground formed.
By the embodiment 6 that adhesive resin replaces with DPHA from PETA, obtain roughly good physical property, though but be coated face roughly uniformity, have a little coarse, and mar resistance declines a little.In addition, DPHA is replaced with trimethylolpropane triacrylate (TMPTA) and tetramethylol methane tetraacrylate (PETTA), when making antireflection film, confirm to obtain the result almost identical with embodiment 6.In the embodiment 7 that the content of fluorochemicals is many, obtain roughly good physical property, though but be surface state roughly uniformity, have some coarse, and mar resistance declines a little.Glycol ethers as solvent is replaced with in the embodiment 8 of toluene, infers there are some impacts to the dispersiveness of particulate, although mar resistance has some decline, obtain roughly good result.Can confirm ketone, glycol ethers good as solvent result of use according to result.In addition, the embodiment 9 that the material used by patent documentation 2 uses as fluorochemicals, although obtain at stain-proofing layer without island structure, good sample without slight albefaction, but the flatness of coated surface is poor and confirm slight deformation.Can confirm that fluorochemicals preferably has silane unit thus.
In addition, infer that in the antireflection film of embodiment gained, the total of the thickness of low-index layer and stain-proofing layer is about 100nm, and the thickness of stain-proofing layer is in the scope of 1 ~ 3nm.
On the other hand, in the poor comparative example 1 of fluorochemicals, although preventing reflection characteristic and embodiment are equal, because silicon composition is many, insufficient in soil resistance, also confirm albefaction.In addition, landing angle is 33 ° can not be called the surface with uniformity, confirms island structure from the observations by atomic force microscope.Can think that this island structure is because fluorine containing silane compound is few, the outmost surface of low-index layer cannot be coated to completely, the stain-proofing layer of uniformity cannot be formed, thus occur, can think that this is the main cause becoming slight albefaction.Excessively comprise in the comparative example 2 of fluorochemicals, in low-index layer entirety, excessive being separated occurs, the surface integral of low-index layer is coarse significantly, does not form the stain-proofing layer of uniformity.Can think this coarse be that excessive fluorochemicals produces concavo-convex with the teat of the particulate in low-index layer for opportunity, result the surface integral of layer occur coarse.And the amount of the fluorochemicals because average surface roughness is large, contained by stain-proofing layer is many, this stain-proofing layer can become soft, when doing wiping when evaluating soil resistance, will cause scar.In addition, do not comprise fluorochemicals, fluorine atom/carbon atomic ratio is less than in the comparative example 3 of 0.6, although obtain the surface of uniformity, because the amount of fluorine is few, soil resistance is also insufficient.Comparative example 4 is the examples not using particulate, because the intermiscibility of adhesive resin and fluorochemicals is poor, causes film entirety to bleach when dried coating film, cannot evaluate.According to such result, known in order to keep the balance between the fluorochemicals of adhesive resin and intermiscibility difference, reach the formation of final purpose, the effect of particulate is indispensable.In addition, formed in the comparative example 5 of stain-proofing layer by evaporation, soil resistance and surface state are roughly good, but due to do not have to occur as of the present invention antifouling mutually in reactive functional groups and low-refraction mutually in some reactive functional groups react and solidify, stain-proofing layer after solidification and the adaptation of low-index layer weak, mar resistance be deteriorated.
Industry utilizes possibility
According to the present invention, easily can manufacture and there is excellent preventing reflection characteristic, there is excellent mar resistance and soil resistance, and suppress so far never by the antireflection film of the generation of slight albefaction bothered about.The antireflection film of gained is applicable to being arranged at polarization plates, image display device.

Claims (13)

1. the manufacture method of an antireflection film, it comprises following operation (1) ~ (3) successively, and this antireflection film has transparent base, low-index layer and stain-proofing layer at least successively, from fluorine/carbon that this stain-proofing layer side is measured by X-ray photoelectron spectroscopy XPS, in atom number ratio, be 0.6 ~ 1.0, and silicon/carbon, in atom number ratio, be less than 0.25, the average surface roughness Ra ' of this stain-proofing layer is below 10nm, wherein
Operation (1) is the operation being coated with low-index layer formation composition over the transparent substrate thus forming film, and described low-index layer formation composition is at least containing fluorochemicals, particulate and adhesive resin;
Operation (2) is the operation making this film be separated into low-refraction phase and antifouling phase;
Operation (3) is this low-refraction phase of heating and this antifouling phase, or irradiates ionizing ray mutually to this low-refraction phase and this are antifouling, thus forms the operation of the stain-proofing layer of whole of low-index layer and this low-index layer coating.
2. the manufacture method of antireflection film as claimed in claim 1, wherein, fluorochemicals is containing having the silane unit of reactive group and having the material of silane unit of holo-fluorine polyester.
3. the manufacture method of antireflection film as claimed in claim 2, wherein, has the silane unit of reactive group and has the silane unit of holo-fluorine polyester, having siloxane backbone respectively.
4. the manufacture method of antireflection film as claimed in claim 2 or claim 3, wherein, reactive group is selected from least one in (methyl) acryloyl group and vinyl.
5. the manufacture method of the antireflection film according to any one of claims 1 to 3, wherein, the weight-average molecular weight of fluorochemicals is more than 5000.
6. the manufacture method of the antireflection film according to any one of claims 1 to 3, wherein, particulate is silicon dioxide microparticle.
7. the manufacture method of the antireflection film according to any one of claims 1 to 3, wherein, particulate comprises the particulate with space.
8. the manufacture method of the antireflection film according to any one of claims 1 to 3, wherein, particulate is surface treated particulate.
9. the manufacture method of the antireflection film according to any one of claims 1 to 3, wherein, adhesive resin is ionizing ray curable resin.
10. the manufacture method of antireflection film as claimed in claim 9, wherein, ionizing ray curable resin comprises 3 officials can above (methyl) acrylate.
11. 1 kinds of antireflection films, it is manufactured by the manufacture method of the antireflection film according to any one of claims 1 to 3.
12. 1 kinds of polarization plates, it at least one side of polarizing coating, has antireflection film and this antireflection film is the polarization plates of antireflection film according to claim 11.
13. 1 kinds of image display devices, it has antireflection film or polarization plates in the outmost surface of display, and described polarization plates is the polarization plates at least one side of polarizing coating with antireflection film, and described antireflection film is antireflection film according to claim 11.
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