CN103765249A

CN103765249A - Method for producing antireflection film, antireflection film, polarizing plate, and image display device

Info

Publication number: CN103765249A
Application number: CN201280023924.2A
Authority: CN
Inventors: 筱原诚司; 林真理子; 秋山健太郎
Original assignee: Dai Nippon Printing Co Ltd
Current assignee: Dai Nippon Printing Co Ltd
Priority date: 2011-05-16
Filing date: 2012-05-16
Publication date: 2014-04-30
Anticipated expiration: 2032-05-16
Also published as: TW201303347A; TWI530707B; CN103765249B; KR101725585B1; KR20140037080A; JP6040936B2; JPWO2012157682A1; WO2012157682A1

Abstract

The present invention provides a production method for the easy production of an antireflection film which has excellent antireflection properties, excellent scratch resistance, and antifouling performance and with which the occurrence of faint whitening that has thus far not been addressed is controlled, as well as an antireflection film, and a polarizing plate and image display device that use the film. The production method for producing an antireflection film involves performing, in the following order, a step (1) for forming a coating film by applying, on a transparent substrate, a composition containing at least a fluorine-containing compound, microparticles, and a binder resin and that is for forming a low-refractive-index layer, a step (2) for phase separation of the coating film into a low-refractive-index phase and an antifouling phase, and a step (3) for forming a low-refractive-index layer and an antifouling layer for covering the entire surface of the low-refractive-index layer by heating the low-refractive-index phase and the antifouling phase, or by exposing the low-refractive-index phase and the antifouling phase to ionizing radiation. In the production method, at least a transparent substrate, a low-refractive-index layer, and an antifouling layer are formed in that order, and the fluorine atom/carbon atom ratio measured by X-ray photoelectron spectroscopy (XPS) from the antifouling layer side is between 0.6 and 1.0, the silicon atom/carbon atom ratio is less than 0.25, and the average surface roughness of the antifouling layer (Ra') is 10 nm or less.

Description

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

Technical field

The present invention relates to manufacture method, antireflection film, polarization plates and the image display device of antireflection film.

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), for the preventing reflection characteristic reflecting due to the light of giving high surface hardness or preventing from irradiating from the external light source such as incandescent lamp, fluorescent light, antireflection film is set.Conventionally, antireflection film is the film with the formation that is laminated with hard conating and low-index layer on transparent base, and this low-index layer, in order to contribute to antireflection, is preferably more low-refraction.In addition, as the method that is used for realizing antiradar reflectivity, such as known elder generation on above-mentioned hard conating by the refractive indexes such as middle index layer, high refractive index layer higher be stacked as layer by layer film, then form the method for above-mentioned low-index layer.For example in patent documentation 1, the antireflection film that contains specific particulate in refractive index inhibition layer is disclosed in addition.

On the other hand, as the desired performance of antireflection film, can enumerate the mar resistance of above-mentioned display surface, or be difficult for being made dirty because of fingerprint or sebum, marking pen etc., even and if adhere to these dirts also easily wiping, i.e. soil resistance.As the method for giving antireflection film soil resistance, there is the method (for example patent documentation 1) of using the anti fouling agents such as fluorine-containing anti fouling agent.Yet, patent documentation 1 is in order to suppress to result from hydraulic performance decline containing the gonorrhoea of anti fouling agent composition etc., and improve with said composition in the mutual solubility of each composition, must use weight-average molecular weight to be less than the low-molecular-weight fluorine-containing anti fouling agent of 5000 left and right, the soil resistance that cannot claim gained is abundant.

As the method for giving soil resistance, also proposed in being arranged at its surperficial stain-proofing layer, the fluorochemicals by use with perfluoroalkyl etc., makes, in the relation with element silicon, carbon and fluorine element, to have the method (for example patent documentation 2) of the fluorine atom of specified quantitative.Knownly at patent documentation 2, use, the fluorochemicals with perfluoroalkyl etc., though be the material of soil resistance excellence, but with other material that forms stain-proofing layer, for example the mutual solubility of adhesive resin is poor, thereby the wish coating resin combination that comprises this fluorochemicals is while forming stain-proofing layer, is sometimes difficult to form stable stain-proofing layer, or also has the situation that albefaction problem occurs.

From this point, in patent documentation 2 due to the obvious variation of the mutual solubility with other composition, in order not cause coated face that the harmful effects such as depression or inequality, albefaction occur, in the relation with element silicon, carbon and fluorine element, the fluorine atom of specified quantitative is existed, and obtain certain mutual solubility, thereby form stain-proofing layer, the generation (patent documentation 2, paragraph [0039]) of wishing to form stable stain-proofing layer or suppressing albefaction.

Follow in recent years the high performance of display described above, antireflection film is also pursued high performance, especially the requirement of albefaction is improved.In the past, if spoken parts in an opera refers to the albefaction of degree that can the such reduction film transparency of a glance identification, and what pursue was exactly to reduce this albefaction.Yet in recent years, except albefaction in the past, the slight albefaction that also requires inhibition never to be bothered about so far, this slight albefaction is for to think at first blush having in the film of high transparent, the albefaction of the affiliated technical field personnel degree that ability order is known reluctantly, by patent documentation 2, having coated surface is not uniformity and have the situation etc. of some deformation, have cannot be fully completely corresponding situation.

In addition, as the method for giving film soil resistance, proposed arranging on the hyaline membrane base material of anti-reflection layer, the silane coupling agent that evaporation contains holo-fluorine polyester for example, to form the method (patent documentation 3) of stain-proofing layer.The method that this patent documentation 3 is recorded, the fluorochemicals because described above with perfluoroalkyl etc., poor with the intermiscibility of other material of common formation stain-proofing layer, the resin combination that comprises fluorochemicals as this is difficult to be coated with to form stain-proofing layer, thereby attempt adopting and do not use the just method of the cambial so-called evaporation of energy of other material, wish the stain-proofing layer masking that comprises this fluorochemicals.Yet, owing to adopting evaporation to form layer, therefore just cannot use other materials such as adhesive resin, due to the layer intensity of stain-proofing layer or with the adaptation variation 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, thereby there is hyaline membrane base material to shrink because of heating, or in the activated deterioration test carrying out at the goods for before circulation, there is the problems such as decomposition in the base material itself that is subject to fire damage because of high temperature deposition.

Stain-proofing layer generally makes its thickness reach the stages such as nm, make it thin in the extreme, thereby except excellent soil resistance, also must suppress the generation of slight albefaction, in order to meet these conditions simultaneously, can think except using the material each other with intermiscibility as the composition that forms stain-proofing layer, also must further research and develop and could realize.

[patent documentation 1] TOHKEMY 2010-152311 communique

No. 2008/38714 open text of [patent documentation 2] International Publication

[patent documentation 3] TOHKEMY 2001-188102 communique

Accompanying drawing explanation

Fig. 1 means the schematic diagram of the section of antireflection film of the present invention.

Fig. 2 means the schematic diagram of the section of antireflection film of the present invention.

Fig. 3 means the schematic diagram of the section of antireflection film of the present invention.

Fig. 4 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of embodiment 1 gained.

Fig. 5 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of embodiment 2 gained.

Fig. 6 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of embodiment 3 gained.

Fig. 7 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of embodiment 4 gained.

Fig. 8 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of embodiment 5 gained.

Fig. 9 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of comparative example 1 gained.

Figure 10 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of comparative example 2 gained.

Figure 11 is that pattern picture and the phase place picture of atomic force microscope gained are passed through in the surface of the antireflection film of comparative example 3 gained.

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, provide under this situation, can easily manufacture and there is excellent preventing reflection characteristic, there is excellent mar resistance and soil resistance, and suppress manufacture method, the antireflection film of antireflection film of generation of the slight albefaction never bothered about so far and polarization plates and the image display device that uses this film.

Technological means

The inventor etc. are attentively research to achieve these goals and repeatedly, found that while forming stain-proofing layer according to the method for patent documentation 2, sometimes on its surface, form the inhomogeneous existence of solidfied material of the composition of stain-proofing layer, or circular or the inhomogeneous existence in oval-shaped hole, thereby the island structure that the lower floor that can see base material etc. exposes, the generation of this structure produces and hinders forming stable stain-proofing layer, and then causes occurring the slight albefaction never bothered about so far.; the disclosed method of patent documentation 2; by the fluorine atom of specified quantitative is existed; obtain certain intermiscibility; though improve thus the easiness that forms stain-proofing layer, under the situation of more high performance of pursuing antireflection film, whether form for stain-proofing layer uniformity; whether generate island structure, slight albefaction occurs, also have the further leeway of research.

Therefore, the discoveries such as the inventor, and unlike sought to improve intermiscibility in the past, but the low-index layer formation composition that specially contains by use the specific fluorochemicals that comprises the poor fluorine atom of more intermiscibility, and adopt the method that after coating said composition, it is separated, to be formed layer by said composition by the mode of overlay film surface integral, thereby the generation that can obtain island structure described above has obtained the little and low-index layer of uniformity of the average surface roughness that suppresses, thereby has solved above-mentioned problem.

In addition, although the many fluorochemicals soil resistance excellences of fluorine atom content because intermiscibility is poor, were never considered to contain to use in resin combination, yet can be used this fluorochemicals in the present invention, and can obtain extremely excellent soil resistance in the past.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/carbon atomic ratio of measuring 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 that at least contains fluorochemicals, particulate and adhesive resin on transparent base, forms the operation of filming,

Operation (2) is filmed this and is separated into the operation of low-refraction phase and antifouling phase,

Operation (3) heats this low-refraction phase and this antifouling phase, or to the antifouling ionizing ray that irradiates mutually of this low-refraction phase and this, forms the operation of the stain-proofing layer of whole of low-index layer and this low-index layer of coating;

[2] antireflection film, the manufacture method manufacturing of the antireflection film that it is recorded by above-mentioned [1];

[3] polarization plates, it is to have antireflection film at least one side of polarizing coating, this antireflection film is the antireflection film that above-mentioned [2] are recorded; And

[4] image display device, it is that outmost surface at display has antireflection film or polarization plates, and this polarization plates is at least one side of polarizing coating, to have the polarization plates of antireflection film, and this antireflection film is the antireflection film that above-mentioned [2] are recorded.

Invention effect

According to the present invention, can easily obtain thering is excellent preventing reflection characteristic, thering is excellent mar resistance and soil resistance, and the antireflection film of the generation of the slight albefaction that inhibition is never bothered about so far, and can access polarization plates and the image display device that uses this antireflection film.

Embodiment

[manufacture method of antireflection film]

The manufacture method of antireflection film of the present invention is to manufacture the method for antireflection film, comprise successively operation (1) is coated with and at least contains fluorochemicals on transparent base, the low-index layer formation composition of particulate and adhesive resin, thereby form the operation of filming, operation (2) is filmed this and is separated into the operation of low-refraction phase and antifouling phase, and operation (3) heats this low-refraction phase and this antifouling phase, or to the antifouling ionizing ray that irradiates mutually of this low-refraction phase and this, form the operation of the stain-proofing layer of whole of low-index layer and this low-index layer of coating, described antireflection film has transparent base at least successively, low-index layer, and stain-proofing layer, fluorine atom/carbon atomic ratio of measuring 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 and the antifouling phase that in operation (2), form, at coating low-index layer, to form the phase of the interior formation of filming forming with composition, it is uncured state with the adhesive resin in composition that low-index layer forms, in addition, the solvent preferably comprising in said composition, under the degree being separated in vaporized state.On the other hand, these are mutually by through operation (3), are formed on that in this layer, adhesive resin becomes solid state, solvent evaporates and more than half non-existent low-index layer and stain-proofing layer.Therefore, in the present invention, the state being present in filming is called to 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 forms the state with composition with the mobility of physics, gets final product viscometric state, solid state refers to that low-index layer forms the state with composition without the mobility of physics, cannot viscometric state.

For each operation, explain below.

(operation (1))

Operation (1) is the low-index layer formation composition that coating at least contains fluorochemicals, particulate and adhesive resin on transparent base, thereby forms the formation operation of filming of filming.

In the present invention, film form operation preferably by preparing transparent base, prepare low-index layer in addition and form and with composition, on this transparent base, be coated with this low-index layer formation and carry out with composition.

(low-index layer forms the preparation with composition)

It is by homogeneous mixing such as fluorochemicals described later, particulate, adhesive resin and the fluoropolymer preferably using or various adjuvants that low-index layer forms with composition, and makes it be dissolved in solvent as required and prepare.

This low-refraction formation composition, if consider, throughput rate is preferably is dissolved in the aqueous of solvent.Aqueous low-index layer forms the viscosity with composition, as long as can form the viscosity of filming on the surface of transparent base by coating method described later, there is no particular restriction.

(formation of filming)

The formation of filming is on the surface of transparent base, so that the thickness after solidifying becomes the mode of the set thickness of aftermentioned, by as above-mentioned and preparation low-index layer formation composition, by intaglio plate be coated with, the known manner of rod coating, roller coat cloth, trans roller coat, comma coating, mould coating etc., preferably by intaglio plate be coated with, mould is coated with and carries out.

Below, for formation transparent base and low-index layer formation, with each composition of composition, describe.

(transparent base)

Transparent base used in the present invention, so long as the transparency using usually used as the base material of antireflection film is not particularly limited, can, according to purposes, suitably select plastic foil, plastic tab etc. yet be preferably.

As this plastic foil or plastic tab, can enumerate the various materials that comprise synthetic resin.As synthetic resin, can enumerate the straight chain shape 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; The vibrin of pet resin (PET), polybutylene terephthalate resin, PEN-m-phthalic acid copolymer resins, polyester based thermoplastic elastic body etc.; The acrylic resins such as poly-(methyl) methyl acrylate resin, poly-(methyl) ethyl acrylate resin, poly-(methyl) butyl acrylate resin; Take the polyamide that nylon 6 or nylon 66 etc. are representative; The cellulose-based resins such as triacetyl cellulose resin (TAC), diacetyl cellulose, acetate butyrate cellulose, cellophane; The cyclopolyolefin resin that norborene, bicyclopentadiene, tetracyclododecen etc. can obtain from cycloolefin; Polystyrene resin; Polycarbonate resin; Polyarylate resin; Or polyimide resin etc.

As transparent base, can be by among above-mentioned plastic foil, plastic tab, with independent form, use or select two or more to make potpourri and use, viewpoint from 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 5～1000 μ m left and right, if consider permanance or operability etc., is preferably 15～80 μ m, more preferably 20～60 μ m.

(low-index layer formation composition)

The low-index layer formation composition using in the present invention is the resin combination that contains fluorochemicals, particulate and adhesive resin.For each composition, explain below.

(fluorochemicals)

In order to form stain-proofing layer at antireflection film of the present invention, low-index layer forms and comprises fluorochemicals with composition.As fluorochemicals used in the present invention, be preferably the compound with reactive group and holo-fluorine polyester, wherein, preferably can enumerate and contain the compound that there is the silane unit of reactive group and there is the silane unit of holo-fluorine polyester.In the present invention, by fluorochemicals, have reactive group, easily the composition of other in composition is combined, thereby can form firmer layer, as a result of, can obtain the not only layer of thin but also excellent scratch resistance.In addition, the excellent scratch resistance of antireflection film outmost surface in the present invention, the while also refers to the adaptation excellence of the Ceng Yuqi lower floor of outmost surface.; so that low-index layer form with the fluorochemicals in composition low-refraction phase and antifouling in be mutually this antifouling mutually in more the mode of volume exist; while solidifying in aftermentioned operation (3); the reactive group being 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 reacting of the reactive group of this fluorochemicals and the reactive group of adhesive resin or solidifying of adhesive resin itself, thereby further improve the adaptation of stain-proofing layer, and hardness raising, the layer that mar resistance is very excellent comprehensively become.

In addition, the compound that comprises silane unit described above, due to low-refraction in mutually contained particulate there is affinity, on the surface of low-refraction phase, form antifouling phase time, can give the wellability of whole that spreads all over this surface, even in addition because of in solvent from mutually almost the state of evaporation also can keep wellability, so obtain the viewpoint of the stain-proofing layer of uniformity from the whole face on this surface, it is important.And then, because this compound is very soft, improved sliding, so can obtain the layer of excellent scratch resistance.And, because thering is affinity, can obtain sustainedly and stably wellability, thus solvent when evaporation there is depression or generate island structure to be inhibited, thereby by the generation of these slight albefactions, also suppressed.And then, by using the fluorochemicals in same a part with silane unit and perfluor ether, can suppress being separated of silane unit and PFPE, can easily obtain the surface of uniformity more.At this, silane unit is the represented unit of following general formula (1).

In formula (1), X represents singly-bound or oxygen atom, R ¹and R ²the organic group that represents monovalence, and R ¹and R ²in at least one be any monovalent organic radical group that comprises reactive group or holo-fluorine polyester.Fluorochemicals used in the present invention can be for example to have R ¹silane unit and R for any monovalent organic radical group that comprises reactive group ¹for the fluorochemicals of the silane unit of any monovalent organic radical group that comprises holo-fluorine polyester, can also be to there is R ¹for any monovalent organic radical group and the R that comprises reactive group ²fluorochemicals for the silane unit of any monovalent organic radical group that comprises holo-fluorine polyester.In addition, in a plurality of silane unit, R ¹, R ²and X is independently, fluorochemicals of the present invention, as long as at least contain the silane unit with reactive group and the silane unit with holo-fluorine polyester, also can be the compound with multiple silane unit.

In the present invention, these silane unit are preferably the unit with siloxane backbone.Being preferably X in above-mentioned formula (1) is oxygen atom.By fluorochemicals, have siloxane backbone, the affinity of the particulate that itself and low-index layer described above comprise becomes well, thereby can obtain uniformity and have the stain-proofing layer of excellent stain, is not prone to slight albefaction.

The weight-average molecular weight of fluorochemicals (measure with GPC method be scaled poly weight-average molecular weight) is preferably more than 5000, and more preferably 5000～100000, more preferably 5000～50000.The weight-average molecular weight of fluorochemicals, as long as more than 5000 just can obtain excellent soil resistance, as long as just can obtain the good solubility in organic solvent below 100000, thereby is easy to obtain the surface of uniformity.

As reactive group; preferably can enumerate the reactive group of the ethene unsaturated double-bond base with (methyl) acryloyl group, vinyl etc. or epoxy radicals, carboxyl, amino, hydroxyl etc.; the reactive group in these, preferably with the ethene unsaturated double-bond base of (methyl) acryloyl group, vinyl etc.If reactive group is above-mentioned group, can form with the easier combination of other composition in composition with low-index layer, therefore the firmer layer of low-index layer and the adaptation of stain-proofing layer as described above can be formed, the not only layer of thin but also excellent scratch resistance can be obtained, thus preferred.

As holo-fluorine polyester, for example, preferably can enumerate the represented group of following general formula (2).

In formula (2), a～e is 0～50 integer, can be identical also can be different.A～d is preferably integer, e that the weight-average molecular weight of the represented holo-fluorine polyester of formula (2) is become in 200～6000 scope and is preferably 0～2.In addition, xa, xb, xc and xd are 1～4 integers, can be identical also can be different.Xa, xb, xc and xd are 3 and 4 o'clock ,-C _xaf _2xa,-C _xbf _2xb,-C _xcf _2xc, and-C _xdf _2xdcan be straight chain shape and also can be a chain.

The content of the fluorine atom in fluorochemicals is preferably 5～80 mass parts, 10～70 mass parts more preferably, further 20～60 mass parts more preferably.If the content of the fluorine atom in fluorochemicals is more than 5 mass parts, can obtain excellent soil resistance, if below 80 mass parts, can obtain the good solubility in solvent, be therefore easy to obtain the surface of uniformity.

With respect to low-index layer, form total amount (solid constituent) 100 mass parts with the aftermentioned particulate in composition and adhesive resin (also comprising these compositions while using fluorochemical monomer and fluoropolymer), 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, yet normally with the form being contained in solvent, peddle.Now, the amount of these solid constituents is to remove the amount after solvent by the total amount of commercially available product.Though in addition for example Photoepolymerizationinitiater initiater for being contained in one of any solid constituent in composition, while calculating the content of fluorochemicals and be not counted in.

If the content of fluorochemicals is more than 5 mass parts, can be with fluorochemicals by the stain-proofing layer coating of whole of surface with uniformity, therefore there will not be island structure, also slight albefaction do not occur.In addition, if below 30 mass parts, can there is not coated surface unevenness, occur the coarse of concavo-convex etc. coated surface, can obtain the stain-proofing layer of uniformity, slight albefaction can not occur yet, obtain excellent mar resistance.That is,, by making the content of fluorochemicals in above-mentioned scope, can obtain average surface roughness (Ra ') for the uniformity below 10nm, level and smooth stain-proofing layer.

From same reasons therewith, examine rate, the content of fluorochemicals is 5～20 mass parts, more preferably 5～15 mass parts more preferably, further more preferably 10 mass parts as maximum level.By making maximum level, be 10 mass parts, can further make average surface roughness described later (Ra ') for below 5nm, thereby become more level and smooth surface and mar resistance is also good.

(particulate)

Low-index layer forms and contains particulate with composition.Particulate improves preventing reflection characteristic and uses in order to reduce the refractive index of layer.

As particulate, no matter that any of inorganic system, organic system can unrestrictedly be used, from further raising preventing reflection characteristic and guarantee the viewpoint of good skin hardness, viewpoint by material is set out, preferably can enumerate silicon dioxide microparticle, magnesium fluoride particulate etc., with the viewpoint of shape, consider, preferably use spherical and itself there is the particulate in space.In addition, there is the situation in space, conventionally also can use the high alumina particulate of cured film refractive index of specific viscosity mixture resin.

In these, by the viewpoint of material, set out, if consider the preferred silicon dioxide microparticle such as damp and hot permanance.In the present invention, in order to form stain-proofing layer to be coated on whole form of low-index layer, the combination that forms the material of these layers is one of important condition.Because particulate is that the state with roughly fine and closely woven filling exists in whole of the surface of low-index layer, the surperficial proterties of this low-index layer has the tendency of the impact that is subject to particulate.Contained particulate in low-index layer, higher with the affinity of material that forms stain-proofing layer, stain-proofing layer more can easily form to be coated on the mode of whole of this low-index layer.This is because while being separated mutually from low-refraction, this antifouling becoming mutually has wellability and can keep wellability until operation (3) completes at the whole mask in the surface of low-refraction phase when antifouling.From this point of view, particularly preferably particulate is the silicon dioxide microparticle using silicon dioxide as material, and fluorochemicals is silane unit, further for having a combination that siloxane unit comprises the fluorochemicals of silicon atom.

The particulate itself with space, due to externally or inner have a small space, fills the gases such as air such as refractive index 1.0, thereby has the low feature of refractive index of itself.As this particulate with space; can enumerate the poriness particulate, hollow minute particle of inorganic system or organic system etc., such as preferably enumerating porous silica, hollow silica particles or use porous polymer particulate or the Procedure of Polymerized Micro-Particles with Hollow of acrylic resin etc.As the particulate of inorganic system, can enumerate and adopt the silicon dioxide microparticle with space prepared by the disclosed technology of TOHKEMY 2001-233611 communique as preferred example; As the particulate of organic system, can enumerate and adopt Procedure of Polymerized Micro-Particles with Hollow prepared by the disclosed technology of TOHKEMY 2002-80503 communique etc. as preferred example.

Silicon dioxide or the porous silica with space described above, its refractive index is 1.20～1.44 left and right, because refractive index is the common silicon dioxide microparticle of 1.45 left and right lower than refractive index, thereby be preferred from the viewpoint of the low-refraction of low-index layer.

In addition,, as particulate, preferably also can enumerate based on its form, structure, state of aggregation, in the disperse state of film inside, can form in inner and/or surperficial at least a portion the particulate of nanoporous structure.

As this particulate, can enumerate above-mentioned silicon dioxide microparticle, or using increasing specific surface area as object, manufacture and fill with post and surperficial poriness partially absorb slow-release material that various chemical substances form, for catalyzer fixedly the poriness particulate of use or the dispersion of the hollow minute particle that is object for heat-barrier material or dielectric materials or condensed matter etc.As concrete example, for example, can enumerate " NIPSIL (trade name) ", " NIPGEL (trade name) ": Japanese silicon dioxide Industrial Co., Ltd system; Or " COLLOID SILICAUP series (trade name) ": Nissan Chemical Ind Ltd etc.

The mean grain size of the primary particle of particulate is preferably 5～200nm, 5～100nm more preferably, further 10～80nm more preferably.If the mean grain size of particulate is more than 5nm, can obtain excellent refractive index decline effect, if below 200nm, can not damage the transparency of low-index layer 3 and obtain the disperse state of good particulate.In addition, in the present invention if mean grain size in above-mentioned scope, to be 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 to transmission electron microscope (TEM), carry out the observation of any three visual field parts, on photo, actual measurement is present in the diameter of any 20 particles (three visual field parts add up to 60 particles) of this section, is averaged particle diameter.

In addition, the particulate using in the present invention, is preferably surface treated particulate.As surface treatment, preferably can enumerate the surface treatment of using silane coupling agent, wherein, preferably use the surface treatment of the silane coupling agent with (methyl) acryloyl group.By particulate is implemented to surface treatment, improve the affinity with adhesive resin described later, it is even that the dispersion of particulate becomes, be difficult to occur particulate cohesion each other, the transparence that therefore can suppress the low-index layer that causes due to macroparticle declines, or low-index layer forms with the coating of composition, the decline of the coating strength of said composition.In addition; the in the situation that of thering is (methyl) acryloyl group at silane coupling agent, because this silane coupling agent has ionizing ray curability, easily react with adhesive resin described later; therefore at low-index layer, form with in the filming of composition, particulate is fixed by bonding agent resin.That is, particulate has in adhesive resin the function as crosslinking chemical.Thus, can obtain this all tension effect of filming, adhesive resin can retain original flexibility and directly to low-index layer, give excellent skin hardness.Therefore, low-index layer is out of shape by the flexibility of bringing into play itself, thereby has the absorbability of external impact or restoring force, therefore, can suppress the generation of scar, becomes the layer of the high surface hardness with excellent mar resistance.

As the silane coupling agent preferably using in the present invention, 3-(methyl) the acryloxy propyl trimethoxy silicane of can giving an example, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group methyl dimethoxysilane, 3-(methyl) acryloxy propyl group methyldiethoxysilane, 2-(methyl) acryloxy propyl trimethoxy silicane, 2-(methyl) acryloxy propyl-triethoxysilicane etc.

The content of particulate in low-index layer, is preferably 10～95 quality %, 20～90 quality % more preferably, further 30～90 quality % more preferably.At this, the content of particulate in low-index layer, be and the total solid composition of low-index layer with composition, on fluorochemicals, particulate and adhesive resin, the content of adding the particulate in the total amount (total amounts of all compounds beyond the solvent comprising 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 %, can fully obtain using the effect of above-mentioned particulate, if below 95%, can reduce the average surface roughness (Ra ') of stain-proofing layer, can also, with resin by filling and leading up well between particulate gap each other, obtain excellent skin hardness.

In addition, the raising mar resistance of take in the present invention is object, can use the solid particulate without space simultaneously.The mean grain size of the primary particle of this solid particulate is preferably 1～200nm, 1～100nm more preferably, further 5～20nm more preferably.If 1nm is little with the next contribution to raising skin hardness, if 200nm can damage the transparency of low-index layer above, be difficult to obtain good microparticulate state.

The content of solid particle is as long as suitably adjust according to the desired mar resistance of low-index layer, refractive index etc.For example the total quality with the total solid composition of composition with respect to low-index layer, is preferably 1～30 quality %, more preferably 5～20 quality %.

From the viewpoint of mar resistance, the transparency, wish similarly to carry out surface treatment with the above-mentioned particulate with space.

As solid particle, can use the known solid particle that is used in antireflection film or hard coat film etc. in the past.As commercially available product, for example preferably can enumerate the trade name MIBK-ST (average primary particle diameter: 12nm) and MIBK-ST-ZL (average primary particle diameter: 88nm), or wave day such as the trade name OSCAL series (average primary particle diameter: 7～100nm) etc. that catalyst changes into industry (strain) system of daily output chemical industry (strain) system.

(adhesive resin)

From the viewpoint of film forming and film strength etc., low-index layer forms and contains adhesive resin with composition.As adhesive resin, preferably can enumerate can be by solidifying with the ionizing ray of heating or irradiation ultraviolet radiation, electron beam etc., thus make headed by above-mentioned fluorochemicals, particulate, as required and other one-tenth adding grade low-index layer layer in immobilized resin.In addition, in the present invention, the preferred resin low with the intermiscibility of this fluorochemicals, thus can make above-mentioned fluorochemicals be separated efficiently, obtain the stain-proofing layer of complete coating low-index layer.

More specifically, as adhesive resin, such as preferably enumerating heat-curing resin or the ionizing ray curable resins such as melamine series, urea system, epoxy system, ketone system, diallyl phthalate system, unsaturated polyester (UP) system and phenol system.Wherein, preferred ionizing ray curable resin.

So-called ionizing ray curable resin is intrafascicular at electromagnetic wave or charged particle, has the resin of the quanta of energy that can make molecule aggregation, by irradiation ultraviolet radiation or electron beam etc., curing resin can occur.Particularly, can be from suitably select among habitual polymerizable monomer and polyreactive oligomers (or prepolymer) to use as the resin of ionizing ray curability in the past.

As polymerizable monomer, be suitably for (methyl) acrylate monomer in molecule with free-radical polymerised unsaturated group, wherein preferred multi-functional (methyl) acrylate monomer.

As multi-functional (methyl) acrylate monomer, so long as there is (methyl) acrylate monomer of 2 above ethene unsaturated links in molecule, there is no specific limited.Particularly can preferably enumerate (methyl) acrylate of 2 officials' energy such as ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate monostearate, two cyclopentene two (methyl) acrylate, isocyanuric acid ester two (methyl) acrylate; (methyl) acrylate of 3 officials' energy such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester; 4 officials such as pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate can be above (methyl) acrylate; The oxirane modifier of above-mentioned multi-functional (methyl) acrylate monomer, caprolactone modification thing, propionic acid modifier etc.

In these, from obtaining the viewpoint of excellent mar resistance, (methyl) acrylate that preferably 3 officials can be above.These multi-functional (methyl) acrylate monomers can be used separately a kind, also can combine two or more use.More specifically, in the present invention, can obtain aptly the effect material of the objects such as soil resistance, mar resistance (adaptation), anti-slight albefaction, be preferably (methyl) acrylate of 3 officials' energy such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, three (acryloxy ethyl) isocyanuric acid ester; 4 officials such as pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate can be above (methyl) acrylate, pentaerythrite three (methyl) acrylate particularly preferably.

In the present invention, when stating in the use multi-functional (methyl) acrylate monomer, in order to reduce its viscosity etc., can be in not damaging the scope of object of the present invention, suitably also with simple function (methyl) acrylate monomer.In addition,, for by increasing the suitable adjustment coating of viscosity and preventing the warpage due to cure shrinkage, can use following polyreactive oligomers or polymkeric substance.

Below, as polyreactive oligomers, can enumerate the oligomer in molecule with free-radical polymerised unsaturated group, such as oligomer of epoxy (methyl) acrylic ester, carbamate (methyl) acrylic ester, polyester (methyl) acrylic ester, polyethers (methyl) acrylic ester etc.

In addition, in the present invention, for example also can use polymerization methyl methacrylate and glycidyl methacrylate in advance to obtain multipolymer, then make the glycidyl of this multipolymer and methacrylic acid or acrylic acid carboxyl condensation and the reactive polymer that obtains.This reactive polymer can be obtained with commercially available product form, as commercially available product such as enumerating " MACROMONOMER (trade name) ": Toagosei Co., Ltd's system etc.

In the present invention, can preferably use uv curing resin or electronic beam curing resin as ionizing ray curable resin.

While using uv curing resin as ionizing ray curable resin, with respect to this uv curing resin of 100 mass parts, preferably add the Photoepolymerizationinitiater initiater of 0.5～10 mass parts left and right, more preferably add 1～5 mass parts.As Photoepolymerizationinitiater initiater, can be from suitably select habitual product in the past, be not particularly limited, for example, for thering is the polymerizable monomer or polyreactive oligomers of free-radical polymerised unsaturated group in molecule, can enumerate 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.These can be any separately, or two kinds of combinations and using.These Photoepolymerizationinitiater initiaters can commercially available product form be obtained, for example, can enumerate " IRGACURE184 (trade name) ", " IRGACURE907 (trade name) " " IRGACURE127 (trade name) " (being Ciba (strain) system) etc.

With respect to low-index layer, form by total solid composition 100 mass parts in composition, the content of adhesive resin is preferably 0.5～20 mass parts, more preferably 1～15 mass parts.If the content of adhesive resin, in above-mentioned scope, can obtain excellent mar resistance, can make fluorochemicals be separated efficiently.

(fluoropolymer)

From reducing the viewpoint of refractive index, low-index layer used in the present invention forms and is preferably and comprises fluoropolymer with composition.As fluoropolymer, such as preferably enumerating (methyl) acrylic acid part and completely fluorinated alkyl, thiazolinyl, aryl ester class, fluorinated vinyl ethers, fluorinated vinyl ester class, fluorinated vinyl ketone etc. wholly or in part wholly or in part wholly or in part.

In addition, as fluoropolymer, be preferably the material that also comprises silicon except fluorine, for example, preferably can enumerate the vinylidene fluoride copolymers that contains silicone that contains silicone composition in multipolymer.Silicone composition as this situation, can enumerate (gathering) dimethyl siloxane, (gathering) di-ethyl siloxane, (gathering) diphenyl siloxane, (gathering) methyl phenyl siloxane, alkyl-modified (gathering) dimethyl siloxane, (gathering) dimethyl siloxane that contains azo group, or dimethyl silicone, phenymethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, hydrogenated methyl silicone, the silicone that contains silanol group, the silicone that contains alkoxy, the silicone that contains phenolic group, methacryl modified silicone, acryloyl group modified silicone, amino modified silicone, carboxyl acid modified silicone, methyl alcohol modified silicone, epoxide modified silicone, sulfhydryl modified silicone, fluorine modified silicone, polyether modified silicone etc.Wherein preferably there is the material of dimethyl silica alkyl structure.

In addition, except above-mentioned, also can use the compound at least in molecule with 1 isocyanate group and fluorine, with the compound that at least there is the compound with the functional group of isocyanates radical reaction such as 1 amino, hydroxyl, carboxyl in molecule and react gained; 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 the compound etc. of gained 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, due to the good solubility that can obtain in solvent, therefore process easily.In addition, if below 1.45, can make the refractive index of the low-index layer of formation be reduced to required scope.

This fluoropolymer can obtain with commercially available product form, for example preferably can enumerate OPSTAR TU2181-6, OPSTAR TU2181-7, OPSTAR TU2202, OPSTAR JN35, the OPSTAR TU2224 of JSR company system, OPTOOL AR110, the OPTOOLAR100 etc. of DAIKIN industrial group system.

With respect to low-index layer, form by total solid composition 100 mass parts in composition, the content of fluoropolymer is preferably 1～30 mass parts, more preferably 5～25 mass parts.If the content of fluoropolymer, in above-mentioned scope, can reduce refractive index efficiently.

(fluorochemical monomer)

From reducing the viewpoint of refractive index, low-index layer used in the present invention forms and is preferably and comprises fluorochemical monomer with composition.From solidifying to form efficiently low-index layer and can obtaining the viewpoint of excellent hardness, fluorochemical monomer is preferably has 2 above reactive functional groups in 1 molecule.As this fluorochemical monomer, preferably can enumerate have pentaerythrite skeleton fluorochemical monomer, have dipentaerythritol skeleton fluorochemical monomer, have trimethylolpropane skeleton fluorochemical monomer, have cyclohexyl skeleton fluorochemical monomer, there is the fluorochemical monomer of straight chain shape skeleton etc.In these, preferably there is the compound of pentaerythrite skeleton.

The refractive index of fluorochemical monomer is preferably 1.35～1.48, and more preferably 1.37～1.45.If the refractive index of fluorochemical monomer is more than 1.35, can obtain the good solubility in solvent, so process easily.If below 1.48, can make the refractive index of formed low-index layer be reduced to required scope in addition.

This fluorochemical monomer can obtain with commercially available product form, such as preferably can enumerate Kyoeisha Chemical Co., Ltd.'s system the LINC3A with pentaerythrite skeleton, there is the LINC series such as LINC102A of cyclohexyl skeleton etc.

With respect to low-index layer, form by total solid composition 100 mass parts in composition, the content of fluorochemical monomer is preferably 1～30 mass parts, more preferably 3～20 mass parts.If the content of fluorochemical monomer, in above-mentioned scope, can reduce refractive index effectively.

(various adjuvant)

Low-index layer used in the present invention forms with in composition, can, according to required physical property, coordinate various adjuvants.As adjuvant, such as preferably enumerating weatherability modifying agent, mar proof improving agent, polymerization inhibitor, crosslinking chemical, infrared absorbent, cementability improving agent, antioxidant, levelling agent, thixotropy imparting agent, coupling agent, plastifier, defoamer, filling agent, solvent etc.

(solvent)

In addition, as forming at low-index layer the solvent preferably using with in composition, be not particularly limited, still, such as preferably enumerating 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 list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, dihydroxypropane single-ethyl ether, or their potpourri etc.In these, preferred ketone, the glycol ethers high with fluorochemicals affinity, particularly preferred solvent is methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters.By being used alone or as a mixture these, can maintain the dispersiveness of each compound in composition, and can in the operation that is separated (2), complete being aptly separated of low-refraction phase and antifouling phase.

In addition, use the situation of ketone or glycol ethers solvent in addition, preferably contain ketone or glycol ethers and be the more than at least 50% of total solvent amount, be preferably more than 70%.Particularly in the situation that using ketone, because forming with the coating of composition, improves low-index layer, and because the evaporation rate of solvent appropriateness after the coating of said composition is difficult for occurring uneven drying, in addition, can follow the evaporation of solvent, make efficiently fluorochemicals be separated, the large area that therefore can easily obtain uniformity film (stain-proofing layer).

The amount of solvent according to can uniform dissolution, disperse each composition, the mode of concentration that can be not excessive rarefied when not condensing and being coated with during preservation after composition preparation is suitably adjusted.Low-index layer forms and is preferably 50～99.5 quality % with the content of the solvent in composition, is preferably set to 70～98 quality %.By being made as this content, can obtaining dispersion stabilization excellent especially, and be applicable to the long-term composition of preserving.In addition, at low-index layer, form with the solvent using in composition, owing to passing through carried out dry or curing evaporation after coating said composition, be therefore present in low-index layer hardly.

(operation (2))

Operation (2) is the operation that filming of making to form in above-mentioned operation (1) is separated into low-refraction phase and antifouling phase.As the method that promotes to be separated, such as preferably can enumerating the method that heats of making to film in air, the heating means of method etc. such as remain in steam or in autoclave.In addition, also can not heat etc., simply place until be separated.

In the present invention, at coating low-index layer, form with after composition, and make before adhesive resin in said composition solidifies, in this operation by heating described above or simply place, the fluorochemicals in said composition can become easy emersion in the outmost surface side of filming (with transparent base be opposition side).Consequently at low-index layer, form with in the filming of composition, much more relatively the content that is separated into fluorochemicals show the antifouling phase of soil resistance, the relative low-refraction phase that shows less low-refraction of content with fluorochemicals, and antifoulingly heat mutually or irradiate ionizing ray what form in outmost surface side, the mode of whole with coating low-index layer forms stain-proofing layer, can obtain excellent soil resistance thus.; in the present invention, being coated with low-index layer formation forms while filming with composition; can in filming, this be separated into two phases; this is filmed and has low-refraction phase and antifouling phase; by process operation described later (3); two-phase each self-forming low-index layer and stain-proofing layer, and then in other words, also can say and form the low-index layer with stain-proofing layer.

Heating described above or simple time of placing, as long as fluorochemicals emersion, in the time degree of the outmost surface side of filming, is generally about 1～30 second.

In addition, by heating described above or place merely, also can make low-index layer form with the solvent evaporation preferably comprising in composition, also can this solvent of evaporation as object, be dried energetically.The dry temperature conditions of this situation is preferably the scope of 20～120 ℃, more preferably 40～100 ℃, is preferably 10～180 seconds drying time, more preferably 15～90 seconds.The ceiling temperature of baking temperature can suitably be selected according to the material of the transparent base of use.On the other hand, from fluorochemicals is separated in outmost surface fast and positively, the viewpoint that forms stain-proofing layer is set out, and lower limit temperature is suitable is chosen to be 20 ℃.From stable, make the antifouling viewpoint that is separated mutually, forms stain-proofing layer in addition, be more preferably chosen to be more than 40 ℃.

(operation (3))

Operation (3) is heating filming after being separated, or to the irradiation ionizing ray of filming, and makes this low-refraction phase in filming and antifouling phase become separately the operation of low-index layer and stain-proofing layer.At this, low-index layer is the layer because there is particulate in this layer with preventing reflection characteristic, and stain-proofing layer is the layer because of have fluorochemicals in this layer with soil resistance.In this instructions, for convenient, because comprise comparatively speaking the layer of less fluorochemicals, there is more excellent preventing reflection characteristic, thereby be called low-index layer (heating or irradiate before ionizing ray be low-refraction phase), because comprise comparatively speaking the layer of more fluorochemicals, there is more excellent soil resistance, thereby be called stain-proofing layer (being antifouling phase before heating or irradiation ionizing ray).

The heating of filming is still irradiated to ionizing ray, is according to low-index layer, to form the adhesive resin comprising with composition to select.While adopting heat-curing resin as adhesive resin, select heating process.As heating condition, can coordinate the solidification temperature of used heat-curing resin to do suitable setting, for example can be made as 60～100 ℃.

In addition, while adopting ionizing ray curable resin as adhesive resin, as long as irradiate ionizing ray to filming.While solidifying above-mentioned filming, while using electron beam as ionizing ray, with regard to its accelerating potential, can be according to the thickness of the resin using or layer and suitable selected, be conventionally preferably with accelerating potential 70～300kV left and right cured coating film.

In addition, in the irradiation of electron beam, due to accelerating potential more high-penetration ability more increase, use can be because of the situation of the deteriorated base material of electron beam as base material, by making the penetration depth and the mode selected accelerating potential of the thickness of filming for equating in fact of electron beam, can suppress the unnecessary irradiation of electron beam to base material, can be by the deteriorated bottom line that is controlled at of base material due to excess electrons bundle.

Exposure dose is preferably and makes the cross-linking density of the curable resin in low-index layer is saturated amount, is generally 5～300kGy (0.5～30Mrad), more preferably selected in the scope of 10～50kGy (1～5Mrad).

In addition, as electron beam source, there is no particular restriction, such as using Ke Kelaofu-Wal 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 that pause.

Use ultraviolet ray as the situation of ionizing ray, the ultraviolet ray of being sent by ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc lamp, xenon arc lamp, metal halid lamp etc. such as use etc.The exposure of energy line source, the cumulative exposure amount at ultraviolet wavelength 365nm, is preferably 50～500mJ/cm ²left and right.

From preventing the viewpoint of the surperficial oxygen obstruction of resin combination for low-index layer, ultraviolet irradiation is preferably under nitrogen environment, for example, under the environment below oxygen concentration 1000ppm, carry out.In the present invention after being separated, so that low-refraction phase and antifouling quick-setting viewpoint stably most mutually preferably are ultraviolet ray and irradiate.

In addition,, by solidifying of operation (3), solvent almost evaporates completely, is dried, and in layer, exists hardly.Solvent is large induced evaporation in operation (2), and when operation (2) completes, remains in the solvent in layer, can think almost evaporation 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 there is at least successively transparent base, low-index layer, and the stain-proofing layer of whole of this low-index layer of coating, this low-index layer and this stain-proofing layer are used and contain fluorochemicals, the low-index layer of particulate and adhesive resin forms and forms with composition, fluorine atom/carbon atomic ratio of measuring 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, use Fig. 1～3 to describe.Fig. 1 means the schematic diagram of the section of antireflection film of the present invention, and the 2nd and 3 figure are that the preferred layer with antireflection film of the present invention is configured to example, represent the schematic diagram of its section.The represented antireflection film 1 of Fig. 1 is on transparent base 2, to have low-index layer 3 and stain-proofing layer 8.The represented antireflection film 1 of Fig. 2 is on transparent base 2, to have successively hard conating 4, middle high refractive index layer 7 and low-index layer 3, and the represented antireflection film 1 of Fig. 3 is on transparent base 2, to have successively hard conating 4, middle index layer 5, high refractive index layer 6, low-index layer 3 and stain-proofing layer 8.The layer of antireflection film 1 of the present invention forms, as long as there is successively low-index layer 3 and stain-proofing layer 8 on transparent base 2, be not particularly limited, such as layers such as preferably can enumerating 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 refractive 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 refractive index layer/low-index layer/stain-proofing layer, form.In addition, although do not illustrated, than low-index layer, more approach transparent base side, also can further there is the functional layers such as antistatic layer described later.

(low-index layer 3 and stain-proofing layer 8)

Low-index layer 3 and stain-proofing layer 8 are to use the low-index layer that contains fluorochemicals, particulate and adhesive resin to form the layer forming with composition.These layers are according to the formed layer of the manufacture method of the antireflection film of the invention described above, by be coated with this low-index layer formation on transparent base, with composition, form and film, this is filmed is separated, as the phase of two in filming at this, form low-refraction phase and antifouling phase, by these are filmed, heat or irradiate ionizing ray, forming respectively the layer with stain-proofing layer 8 as low-index layer 3.And, the content of the fluorochemicals comprising in this low-index layer 3, less than the content of the fluorochemicals comprising 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 that show stronger soil resistance.

(low-index layer 3)

For low-index layer 3, its refractive index is being made as N by the refractive index of the layer under being arranged at, and the refractive index of air is made as at 1 o'clock, is N ^1/2situation be most preferred, for example, layer under this low-index layer 3 is while using the formed hard conating of ionizing ray curable resin of widely used multifunctional (methyl) acrylic acid series, if consider, the N of this hard conating is 1.49～1.53, the layer that to be preferably than the refractive index of N low 0.01 be 1.48～1.52.In addition, although refractive index is lower, unreasonablely think, if consider the balance of preventing reflection characteristic and skin hardness, more preferably 1.25～1.45, further more preferably 1.25～1.35.This refractive index can easily be controlled by the kind of particulate and the use amount of content or fluorochemicals etc. thereof.

In addition,, in order to obtain best anti-reflection effect, the thickness of low-index layer 3 and refractive index, preferably meet the relation calculating from following formula (I).

d _A=mλ／(4n _A) (I)

In formula (I), n _athe refractive index that represents low-index layer, m represents positive odd number, is preferably expressed as 1 (air), λ is wavelength, is preferably the value of the scope of 480～580nm.Therefore, in the present invention, from seeking the viewpoint of low-refraction, in above-mentioned formula (I), making m=1 and making λ is the mankind while feeling 480～580nm of the most dazzling wavelength, the refractive index and the thickness that preferably from following formula (II), calculate.

120<n _Ad _A<145 (II)

In refractive index, be preferable range 1.25～1.45 o'clock described above, thickness is preferably about 80nm～120nm.Yet in order to make refractive index ratio lower floor lower to obtain anti-reflection effect, thickness also can be the 120nm～1 μ m left and right that exceeds this scope.In the present invention, be preferably the aggregate thickness of low-index layer and stain-proofing layer within above-mentioned scope.

(stain-proofing layer 8)

Stain-proofing layer 8 be average surface roughness (Ra ') for below 10nm, in the mode of whole on uniformity ground coating low-index layer 3, exist, give the layer of antireflection film soil resistance of the present invention.

This stain-proofing layer 8 is that average surface roughness (Ra ') is the layer below 10nm, and is the layer of uniformity.In addition, the average surface roughness of stain-proofing layer 8 (Ra ') is preferably 0.1～10nm, 0.1～7nm more preferably, and further more preferably mar resistance is brought up to 0.1 the highest～5nm.At this, average surface roughness (Ra ') be by the defined center line average roughness of JISB0601 (Ra), mensuration face is applied and has been carried out the value of three-D expansion, showing as " value that the absolute value of the deviation from reference field to given side is averaged ", is the numerical value of following formula raising.For example, average surface roughness (Ra ') is observed surface configuration as long as can pass through atomic force microscope (AFM), and can utilize subsidiary software for parsing (such as SPIwin etc.) to carry out image analysis to the image of gained and.

R a^{'} = \frac{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 area when smooth (| 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 of measuring the X coordinate of face

Y _b～Y _t: the scope of measuring the Y coordinate of face

Z _o: the average height in mensuration face

Because the average surface roughness of stain-proofing layer 8 is little and uniformity very as mentioned above, there is excellent mar resistance and soil resistance, also there is excellent preventing reflection characteristic, thereby be preferably disposed on the outmost surface of antireflection film of the present invention.

The state of the uniformity of stain-proofing layer 8, not only by this average surface roughness (Ra '), also can pass through that atomic force microscope (AFM) is observed and confirmation particularly.; if stain-proofing layer 8 is observed with atomic force microscope (AFM); in its pattern picture and phase place picture; low-index layer forms and can evenly exist with the solidfied material of composition; or inhomogeneous existence circle or oval-shaped hole in the formed stain-proofing layer of this solidfied material; and the lower floor that makes low-index layer or transparent base etc. exposes the situation that presents island structure and also can not occur, reach the state that spreads all over whole of antireflection film 1 and form.

Fluorine atom/carbon atomic ratio of measuring by X-ray photoelectron spectroscopy (XPS) from stain-proofing layer side is 0.6～1.0, and silicon atom/carbon atomic ratio to be less than 0.25 be necessary.At this, fluorine atom/carbon atomic ratio, silicon atom/carbon atomic ratio are the values according to the ratio of components by fluorine atom, carbon atom and the silicon atom of X-ray photoelectron spectroscopy (XPS) mensuration calculates from the stain-proofing layer side of antireflection film.

The present invention exists more than a certain amount of by the fluorine atom in stain-proofing layer 8, and silicon atom is a certain amount of following existence, by use set fluorochemicals with fixed amount, can obtain showing excellent stain and without the slight antireflection film of albefaction.In addition, because being spreads all over whole and uniformity to form stain-proofing layer, therefore by spreading all over, there is by entire surface above-mentioned atomic ratio, can obtain more excellent soil resistance, reduce the generation of slight albefaction.

From this point of view, fluorine atom/carbon atomic ratio more preferably 0.7～1.0, and silicon atom/carbon atomic ratio more preferably 0.01～0.2.If fluorine atom/carbon atomic ratio is less than 0.6, soil resistance can be insufficient.On the other hand, if be greater than 1.0, the processing of the reagent using in order to realize this numerical value, i.e. the processing of fluorochemicals will become very difficult.In addition, if silicon atom/carbon atomic ratio is more than 0.25, 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 of bringing.

When confirming island structure by atomic force microscope (AFM), or at one Partial Observation to protuberance, average surface roughness is in the situation that the uneven surface beyond scope given to this invention, the atomic ratio of measuring by X-ray photoelectron spectroscopy (XPS) from stain-proofing layer side, in the scope of atomic ratio described above.; at coating low-index layer, form with in the filming of composition gained; be separated into the situation of low-refraction phase and antifouling phase, and then the situation that stain-proofing layer forms as the layer of uniformity on low-index layer, can recently confirm according to determining above-mentioned atom given to this invention; Stain-proofing layer is the situation of the layer of uniformity, also can be according to confirming by the mensuration of atomic force microscope (AFM).Therefore, by stain-proofing layer, having average surface roughness given to this invention and atomic ratio, is except obtaining excellent soil resistance, also can obtain mar resistance and can obtain the antireflection film that slight albefaction does not also manifest.In the present invention, according to the average surface roughness by above-mentioned atomic force microscope (AFM) (Ra '), measure or pattern picture and the observation of phase place picture, and by the atomic ratio that X-ray photoelectron spectroscopy (XPS) is measured, can be used as and determine whether the antireflection film of manufacturing method according to the invention manufacturing or be whether that the evaluation method of antireflection film of the present invention is used.The existence of the stain-proofing layer on low-index layer, although sometimes also can observe by TEM section, if consider layer as thin as a wafer, it is effective stating evaluation method above.In addition, while 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 having not according to the material of each layer due to stain-proofing layer and low-index layer reacts, therefore a little less than adaptation, so mar resistance dies down.That is to say, can evaluate by mar resistance, confirm the difference of manufacture method.At this, mar resistance is evaluated as following evaluation: by steel wool (the Japanese steel wool BONSTAR#0000 processed of Co., Ltd.) is applied to 300g/cm ²above load at the surperficial reciprocating friction of antireflection film 10 times, the visual scar number causing on this surface.

Silicon atom in low-index layer and stain-proofing layer, with SiO ₂, or the form of C-Si-O exist, will be from SiO in the present invention ₂silicon atom be called inorganic silicon atom, the silicon atom from C-Si-O is called to organosilicon atom.Be in the present invention, the silicon atom in low-index layer and stain-proofing layer comprises organic silicon atom and inorganic silicon atom.

Inorganic silicon atom and organosilicon atom, because bond energy is different, think and can in Si2p spectrum, separate appearance.By crest is separated, resolve, near the crest 103～104eV of high bond energy side is decided to be to inorganic silicon atom, near the crest 101～102eV of low bond energy side is decided to be organosilicon atom.Silicon atom in above-mentioned silicon atom/carbon atomic ratio, is made as the numerical value of the total amount of inorganic silicon atom and organosilicon atom.

In the present invention, organosilicon atom/carbon atomic ratio of measuring by X-ray photoelectron spectroscopy (XPS) from stain-proofing layer side is preferably below 0.07, and more preferably 0.01～0.07, further more preferably 0.02～0.06.In addition, inorganic silicon atom/carbon atomic ratio is preferably below 0.2, and more preferably 0.05～0.2, further more preferably 0.08～0.18.If organosilicon atom/carbon atomic ratio, inorganic silicon atom/carbon atomic ratio in above-mentioned scope, can obtain manifesting excellent mar resistance and soil resistance, and there is no the antireflection film of slight albefaction.

In the present invention by meeting above-mentioned atomic ratio, do not need as in the past, to seek to improve the intermiscibility of fluorochemicals, by employing, using low-index layer to form with composition makes the method that the surface integral of low-index layer is separated and forms stain-proofing layer with coating form, this stain-proofing layer suppresses the generation of island structure described above, becomes the layer of the little and uniformity of average surface roughness.

In addition, by use, combine the low-index layer formation composition of fluorochemicals and particulate and adhesive resin, not only can obtain the stain-proofing layer 8 of uniformity, as a result of, can also obtain thering is excellent preventing reflection characteristic, there is excellent mar resistance and soil resistance, and the antireflection film being inhibited of slight albefaction.

So long as level and smooth face just can not occur to cause the contact angle of hexadecane to surpass the situation of 90 ° because forming the organic compound of stain-proofing layer and so in theory.Therefore, contact angle and landing angle can be used hexadecane as measuring liquid, by various commercially available contact angle goniometers, landing angle goniometer, measure.

Antireflection film 1 of the present invention, its outmost surface is made as to the situation of stain-proofing layer 8, the contact angle with respect to surperficial of hexadecane is preferably 55～90 °, more preferably 60～90 °, and the landing angle with respect to surperficial of hexadecane is preferably 1～25 °, more preferably 1～20 °, its outmost surface is uniformity, and stain-proofing layer 8 has level and smooth structure.The fluorochemicals comprising by stain-proofing layer 8 is coated on surface, and contact angle and landing angle be in above-mentioned scope, on the other hand, causes cannot coating surface, uniformity ground time forming island structure, and contact angle and landing angle can be beyond above-mentioned scopes.

The aggregate thickness of low-index layer 3 and stain-proofing layer 8, according to required refractive index and difference, yet from reducing the viewpoint of the reflectivity visible ray field, as mentioned above, is preferably 80～120nm left and right.In addition, 100～120nm more preferably.

Only the thickness of stain-proofing layer 8, infers in the scope of 1～3nm.While analyzing by above-mentioned X-ray photoelectron spectroscopy (XPS), also can detect the atom that the particulate in low-index layer comprises, if and the degree of depth of considering to take the information of X-ray photoelectron spectroscopy (XPS) gained is 1～3nm, 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 mar resistance of antireflection film 1, can have hard conating 4.At this, hard painting refers to the performance that shows the hardness more than " H " in the pencil hardness test with JIS5600-5-4:1999 defined.

Hard conating is preferably the layer that makes ionizing ray curable resin crosslinking curing gained.Form the ionizing ray curable resin of hard conating 4, can be from forming for above-mentioned low-index layer with suitable choice for use among the ionizing ray curable resin of the adhesive resin of composition.The Photoepolymerizationinitiater initiater that ionizing ray curable resin is used while being the situation of uv curing resin, also can be from suitable choice for use illustrational material above.In addition the various adjuvants that, above-mentioned low-index layer formation is used with composition can be used too.

Thickness after hard conating 4 solidifies is the scope in 0.1～100 μ m preferably, the scope of 0.8～20 μ m more preferably, and the further scope of 1～8 μ m more preferably, is particularly preferably the scope of 1.5～4 μ m.As long as thickness in above-mentioned scope, just can obtain the hard performance that is coated with fully, for the impact from outside, be difficult for breaking.In addition, in the present invention, hard conating 4 also can be the layer having concurrently as the function of following middle index layer 5 illustrated or high refractive index layer 6, or has the layer of the 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 can preferably 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 as described above middle index layer 5 and high refractive index layer 6 simultaneously, also can for example with middle high refractive index layer 7 forms, one deck be set 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 (below also referred to as these index layers) preferably can be set arbitrarily in 1.5～2.00 scope.That is, middle index layer 5 is above-mentioned low-index layer 3 height of refractive index ratio at least, 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 the refractive index that is conventionally preferably middle index layer 5 is in 1.5～1.8 scope, the refractive index of high refractive index layer 6 is in 1.6～2.0 scope.

These index layers for example can form by adhesive resin, particulate following with particle diameter 100nm and that have a refractive index of appointment.As the concrete example (representing refractive index in bracket) of the particulate of this refractive index with appointment, can enumerate ZnO (1.90), TiO 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 be from suitable choice for use among above-mentioned adhesive resin.

Preferably the refractive index of the cured film of the refractive index ratio adhesive resin monomer of particulate is high.Because the refractive index of these index layers is normally determined by the containing ratio of particulate, so 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, can form the index layer of the refractive index with appointment.As long as particulate is the particulate with electric conductivity, the index layer that uses this particulate to form will become the layer that has antistatic behaviour concurrently.These index layers can be the vapor-deposited film of the titania that forms 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 that the high inorganic oxide particle of the refractive index of titania and so on is scattered in to the resin of the resin combination that suitable binders resin forms.

The thickness of these index layers is preferably the scope of 10～300nm, 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 hard conating 4 is preferably set on transparent base 2, between hard conating 4 and low-index layer 3, arranges.

(antistatic layer)

From utilizing antistatic effect to obtain the electric conductivity of situation or the viewpoint of electromagnetic shielding effect that anti-dust adheres to or antireflection film of the present invention is used in 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, be preferably low-index layer 3 is arranged to outmost surface, and arrange in the mode in abutting connection with this low-index layer 3.

As antistatic layer, be not particularly limited, for example, preferably can enumerate the formed layer of composition for antistatic layer by containing resin and antistatic agent.

As antistatic agent, be not particularly limited, such as preferably enumerating 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 alkanol compound of tin and titanium and so on; The metal chelate compound of acetylacetonate of this organometallics and so on etc.Also can use the compound that above-mentioned listed compound macromolecule is quantized.

As antistatic agent, also can preferably enumerate and there is tertiary amine base, level Four ammonium or metal-chelating portion, and monomer or oligomer that can be by ionizing ray polymerization or there is the polymerizable compounds such as organometallics of the coupling agent and so on of functional group.These antistatic agent are so long as ionic liquid.

As antistatic agent, also can preferably enumerate electric conductive polymer.As electric conductive polymer, be not particularly limited, such as can enumerate poly-(to phenylene), the polyacetylene of the polypyrrole of heterocycle conjugated system, polythiophene, aliphatics conjugated system of aromatic series conjugated system, containing the polyaniline of heteroatoms conjugated system, in the poly-phenylene vinylene (ppv) of mixed type conjugated system, molecule, have the conjugated system of a plurality of conjugated chains multichain type conjugated system, make the high molecular conductive composite body of aforementioned conjugated polymer chain and saturated macromolecular grafted or block copolymerization etc.

As antistatic agent, also can preferably enumerate conductive metal oxide particulate.As conductive metal oxide particulate, be not particularly limited, for example, 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.

Content as antistatic layer with the antistatic agent in composition does not preferably hinder the above-mentioned suitable cooperation in the scope of the effect of the optical laminate gained of manufacturing according to the present invention when can fully enjoying the effect that contains above-mentioned antistatic agent.

Resin in antistatic layer, as being not particularly limited with the resin of composition for antistatic layer, such as enumerating and the potpourri of ionizing radiation curable resin, ionizing radiation curable resin and the solvent seasoning type resin of the resin-phase having illustrated in the above-mentioned hard conating resin that passes through ultraviolet ray or electronic beam curing together or thermohardening type resin etc.

Antistatic layer can form as follows: on above-mentioned transmitance base material etc., be coated with filming that antistatic layer that each material of above-mentioned use is prepared from forms with composition, for filming, be dried as required, by ionizing ray, irradiate or heating etc. is solidified to form.

[polarization plates]

Polarization plates of the present invention is that at least one side at polarizing coating has antireflection film, this antireflection film is the antireflection film according to the manufacture method gained of the invention described above, , it is characterized by and there is at least successively transparent base, low-index layer, and the stain-proofing layer of whole of this low-index layer of coating, this low-index layer and this stain-proofing layer are used and contain fluorochemicals, the low-index layer of particulate and adhesive resin forms and forms with composition, fluorine atom/carbon atomic ratio of measuring 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 made as such formation, polarization plates of the present invention becomes the element with anti-reflective function of physical strength, excellent in light-resistance, and also cutting down cost significantly, makes display device lightening.

Conventionally 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, can antireflection film of the present invention be set on one side or the two sides of polarizing coating.While being arranged at one side, from improveing the viewpoint of the angle of visibility characteristic of liquid crystal display picture, preferably another side is the optical compensation films (phase retardation film) with the optical compensating layer that comprises optical anisotropic layer.

Situation about using antireflection film of the present invention as diaphragm, as transparent supporting mass, is particularly preferably used tri acetyl cellulose membrane.Now, use the transparent supporting mass of the diaphragm of antireflection film, preferably by the bond layer that comprises polyvinyl alcohol (PVA) etc., be adhered to polarizing coating as required.In addition the opposite side that, is preferably as mentioned above this polarizing coating also has diaphragm, preferably has the formation of above-mentioned optical compensation films (phase retardation film).Also can there is adhering agent layer with the face of the contrary side of polarizing coating of another diaphragm.By being set as such formation, polarization plates of the present invention can be improved the contrast of liquid crystal indicator in bright chamber, angle of visibility up and down.

[image display device]

Image display device of the present invention, outmost surface at display has antireflection film or polarization plates, this polarization plates is at least one side of polarizing coating, to have the polarization plates of antireflection film, this antireflection film is the film according to above-mentioned manufacture method gained of the present invention, be characterized as and there is at least successively transparent base, low-index layer, and the stain-proofing layer of whole of this low-index layer of coating, this low-index layer and this stain-proofing layer are used and contain fluorochemicals, the low-index layer of particulate and adhesive resin forms and forms with composition, fluorine atom/carbon atomic ratio of measuring 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 enumerating displays such as liquid crystal display (LCD), plasma display device (PDP), cathode tube display device (CRT), inorganic and display of organic electroluminescence, rear projection type display, fluorescent display tube (VFD), contact panel, mobile computer, Electronic Paper etc.In addition, as image display device, preferably can enumerate the device that possesses these displays, such as personal computer, personal digital assistant device, game machine, digital camera, Digital Video etc.

Embodiment

Below, by embodiment, further describe the present invention, but the present invention is not limited due to these embodiment.

(evaluation method)

1. minimum reflectivity (evaluation of preventing reflection characteristic)

For the antireflection film at each embodiment and comparative example gained, a side that low-index layer is not set at transparent base sticks to prevent the black belt of the backside reflection of this film, face from low-index layer, use possesses the spectrometer (" UV-2550 (model) ": Shimadzu Seisakusho Ltd.'s (strain) system) measure reflectivity, using the minimum value in wavelength region may 380～780nm as minimum reflectivity of the normal reflection determinator of 5 degree.Minimum reflectivity is less, and the preventing reflection characteristic that expression antireflection film has is more excellent.

2. the evaluation of coated face

Black belt on the film surface label of side that does not form low-index layer, from forming the face of low-index layer, with the visualization of three-wavelength lamp, according to following benchmark evaluation result.

Zero: the face of low-index layer is uniformity.

Δ: the face of low-index layer and above-mentioned zero evaluation comparison, observe 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 at each embodiment and comparative example gained, at steel wool (the Japanese steel wool BONSTAR#0000 processed of Co., Ltd.), applied 300g/cm 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, with BEMCOTM-3 (Asahi Kasei Corporation's system), carry out wiping, with the difficulty of Visual Confirmation wiping, according to following benchmark evaluation.

Zero: wiping fingerprint easily.

Δ: erasable fingerprint.

*: cannot wiping fingerprint.

(2) state while describing with permanent pen on the surface of the antireflection film of each embodiment and comparative example gained with Visual Confirmation, 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, according to following methods, obtain atomic ratio, 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 company system), 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 neutralization, assist under the use with metal mask and analyze.Utilization consists of the atom of carbon atom, nitrogen-atoms, oxygen atom, fluorine atom and the silicon atom on the antireflection film surface of this mensuration gained, calculates fluorine atom/carbon atomic ratio and silicon atom/carbon atomic ratio.In addition, for silicon atom, the separated parsing of crest based on Si2p spectrum, is divided near the inorganic silicon composition (SiO that detects crest 103～104eV ₂), and near 101～102eV, detect the silicone ingredients (C-Si-O) of crest, measure atom and form, calculate inorganic silicon atom/carbon atomic ratio and organosilicon atom/carbon atomic ratio.

6. the evaluation of surface state (mensuration at contact angle and landing angle)

For the antireflection film of each embodiment and comparative example gained, use hexadecane as measuring liquid, utilize analyzer (" DM-500 (model) ", consonance interface science Co., Ltd. system) to measure respectively contact angle and landing angle.Drop amount is decided to be 2 μ l.

7. the evaluation of surface state (evaluation of the surface observation based on atomic force microscope)

Utilize atomic force microscope (AFM) (" L-trace (model) ", SIINANOTECHNOLOGY Co., Ltd. system), with dynamic mode (DynamicForceMode) scanning vibration number: 0.4～1.0Hz, sweep limit: 3 μ m, observe surperficial pattern picture and the phase place picture of the antireflection film of each embodiment and comparative example gained.Cantilever is to use " OMCL-AC160TS-C2 (model) " (KSOLYMPUS Co., Ltd. system, elastic constant: 42N/m).At this, for the cantilever for observing does not reduce resolution because probe pollutes, always use brand-new product.Deteriorated in order to prevent the wearing and tearing when observing in addition, in the scope of not sacrificing resolution, reduce as far as possible carrying out under the condition of the load of probe, carry out the observation in resolution 512 pixel * 256 pixels.After observation, utilize the inclination of attached software correction data.

By this surface observation, when the whole face in the surface of low-index layer is separated and forms stain-proofing layer, can confirm the state of uniformity, on the other hand, on surface, whole face is not separated while forming stain-proofing layer, can confirm that surface is that the part being separated presents island pattern with the inhomogeneous pattern of the part not being separated.At this, so long as the state of uniformity, even if can be described as visually also without slight albefaction, coarse without coated face, form well low-index layer and stain-proofing layer.

Zero: stain-proofing layer uniformity.

Δ: although there is no 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 ')

By above-mentioned atomic force microscope (AFM), observe surface configuration, utilize to resolve and carry out image analysis with software (SPIwin), obtain average surface roughness (Ra ').

Preparation example 1: low-index layer forms the preparation with composition 1

The composition that mixes following composition with following mass ratio, prepares low-index layer and forms with composition 1.

Low-index layer forms 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, the fluorochemicals that contains the silane unit that there is reactive silane unit and there is 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, by surface treatment, has photo-curable reactive group.

* 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, " OPSTAR JN35 (trade name) ", JSR company system, 20 quality % solution (solvents: methyl isobutyl ketone).

* 5, " LINC3A (trade name) ": Kyoeisha Chemical Co., Ltd.'s system, has the fluorochemical monomer of pentaerythrite skeleton, 20 quality % solution (solvents: methyl isobutyl ketone).

* 6, " IRGACURE127 (trade name) ": Ciba (strain) system.

Preparation example 2: hard conating forms the preparation with composition 1

The composition that mixes following composition with following mass ratio, prepares hard conating and forms with composition 1.

Hard conating forms with composition 1

Urethane acrylate ^{* 7}: 15 mass parts

Isocyanuric acid EO modification 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) system.

Embodiment 1

On triacetyl cellulose (TAC) resin molding of thickness 80 μ m, rod coating hard conating forms with composition 1, carry out 50 ℃, 1 minute dry, except after desolventizing, utilize ultraviolet lamp (the FUSION UV SYSTEMS JAPAN light source H-BULB processed of Co., Ltd.), with exposure dose 30mJ/cm ²carry out ultraviolet ray and irradiate, thereby it is solidified, obtain the hard conating of thickness approximately 10 μ m.

Then,, on the hard conating of gained, rod is coated on the prepared low-index layer of preparation example 1 and forms with composition 1, forms film (operation (1)); Implement the heat treated of 50 ℃, 1 minute, making to film is separated into low-refraction phase and antifouling phase, and except (operation (2)) after desolventizing; With exposure dose 200mJ/cm ²carry out ultraviolet ray and irradiate it is solidified, form low-index layer and stain-proofing layer (operation (3)), obtain thering is transparent base, the antireflection film of hard conating, low-index layer and stain-proofing layer.Almost evaporation completely of solvent when curing, the thickness of low-index layer and stain-proofing layer adds up to about 100nm in addition.In addition,, while measuring atomic ratio by X-ray photoelectron spectroscopy (XPS), also detect the contained atom of particulate in low-index layer.If consider, the thickness of X-ray photoelectron spectroscopy (XPS) stain-proofing layer is 1～3nm, infers that the thickness of the stain-proofing layer of gained is in the scope of 1～3nm.

For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope (pattern picture and phase place picture) is shown in to Fig. 4.

Embodiment 2

Except the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 2, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 1 that the results are shown according to above-mentioned evaluation method evaluation.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Fig. 5.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 3, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Fig. 6.

Low-index layer forms 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: high refractive index layer forms the preparation example with composition

In mayonnaise bottle, drop into and mix Titanium Dioxide Rutile Top grade (" TTO51 (C) (trade name) ", Ishihara Sangyo Kaisha, Ltd.'s system, primary particle size: 0.01～0.03 μ m): 10 mass parts, the spreading agent (" DISPERBYK-163 (trade name) " that contains anionic property base, BYK CHEMIE JAPAN company system): 2 mass parts and methyl isobutyl ketone: 48 mass parts, make potpourri.With respect to the potpourri of gained, use the approximately zirconium oxide bead of its 4 times of amounts (φ 0.3mm) with coating vibrating machine, to carry out the stirring of 10 hours, prepare high refractive index layer formation composition.

Preparation example 4: middle index layer forms the preparation example with composition

Except forming at above-mentioned high refractive index layer with in the preparation example of composition, Titanium Dioxide Rutile Top grade is replaced with to the tin oxide (" SN-100P (trade name) " of antimony dopant, Ishihara Sangyo Kaisha, Ltd.'s system), make the spreading agent that contains anionic property base replace with " DISPERBYK-111 (trade name) " (BYK CHEMIE JAPAN company system) in addition, with high refractive index layer form by the preparation example of composition, similarly prepare in index layer formation composition.

Embodiment 4

On triacetyl cellulose (TAC) resin molding of thickness 80 μ m, the above-mentioned hard conating of rod coating forms with composition 1, carry out 50 ℃, 1 minute dry, except after desolventizing, utilize ultraviolet lamp (the FUSION UV SYSTEMS JAPAN light source H-BULB processed of Co., Ltd.), with exposure dose 30mJ/cm ²carry out ultraviolet ray irradiation it is solidified, obtain the hard conating of thickness approximately 10 μ m.

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 ²carry out ultraviolet ray irradiation it is solidified, form the high refractive index layer of the about 120nm of thickness, rod is coated on the high refractive index layer formation composition of preparation example 3 gained, with exposure dose 200mJ/cm ²carry out ultraviolet ray irradiation it is solidified, form the high refractive index layer of the about 60nm of thickness.Then, the following low-index layer of rod coating forms with composition 4, forms film (operation (1)); Implement the heat treated of 50 ℃, 1 minute, making to film is separated into low-refraction phase and antifouling phase, and except (operation (2)) after desolventizing; With exposure dose 200mJ/cm ²carry out ultraviolet ray and irradiate it is solidified, form low-index layer and stain-proofing layer (operation (3)), obtain thering is transparent base, the antireflection film of hard conating, middle index layer, high refractive index layer, low-index layer and stain-proofing layer.Almost evaporation completely of solvent when curing, and the total of the thickness of low-index layer and stain-proofing layer is about 100nm.In addition,, while measuring atomic ratio by X-ray photoelectron spectroscopy (XPS), also detect the atom that is contained in the particulate in low-index layer.If consider, the thickness of X-ray photoelectron spectroscopy (XPS) stain-proofing layer is 1～3nm, and the thickness of inferring the stain-proofing layer of gained is in the scope of 1～3nm.

For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Fig. 7.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 5, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Fig. 8.

Low-index layer forms 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 (solvents: the potpourri of methyl isobutyl ketone and methyl ethyl ketone; photo-curable reactive group: (methyl) acryloyl group, the fluorochemicals that contains the silane unit that there is reactive silane unit and there is holo-fluorine polyester).

Embodiment 6

Except the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 6, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 7, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 8, obtain similarly to Example 1 antireflection film.By the antireflection film for gained, that according to above-mentioned evaluation method, evaluates the results are shown in table 1.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 9, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 1 that the results are shown in of evaluating according to above-mentioned evaluation method.

Low-index layer forms 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) ": SOLVAY SPECIALTY POLYMERS JAPAN Co., Ltd. system, two end 4 officials can methacrylic acid ester modified per-fluoro polyether compound, do not there is the fluorochemicals of silane unit).

* 12, " OPSTAR TU2224 (trade name) ", JSR company system, 20 quality % solution (solvents: methyl isobutyl ketone).

Comparative example 1

Except the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 10, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 2 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Fig. 9.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 11, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 2 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Figure 10.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 12, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 2 that the results are shown in of evaluating according to above-mentioned evaluation method.In addition, atomic force microscope figure (pattern picture and phase place picture) is shown in to Figure 11.

Low-index layer forms 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 the low-index layer in embodiment 1 being formed with composition 1, replace with following low-index layer formation with composition 13, obtain similarly to Example 1 antireflection film.For the antireflection film of gained, by the table 2 that the results are shown in of evaluating according to above-mentioned evaluation method.

Low-index layer forms 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

The fluorochemicals using at embodiment 1 be take to the solution that two benzotrifluorides dilutions are solid component concentration 3 quality %, as anti-soil film vapor deposition source, prepare.

At width: 500mm, thickness: on triacetyl cellulose (TAC) resin molding of 80 μ m, length: 500m, intaglio plate coating hard conating forms with composition 1, intaglio plate is coated with following low-index layer and forms with composition 13, carry out 70 ℃, 1 minute dry, except desolventizing, then with exposure dose 200mJ/cm ²carry out ultraviolet ray irradiation it is solidified, form the hard conating of thickness approximately 10 μ m and the low-index layer of the about 100nm of thickness, obtain having the duplexer of transparent base/hard conating/low-index layer.

Then, above-mentioned anti-soil film vapor deposition source and duplexer are set in coiling type evaporation coating device, vacuum exhaust is to 1e ^-4after Torr is following, start to batch this duplexer with the running speed of 5m/ minute, with the heating fluorescent tube of noncontact heated type, make this anti-soil film vapor deposition source evaporation, obtain forming in the low-index layer side of this duplexer the antireflection film of anti-soil film.For the antireflection film of gained, by the table 2 that the results are shown in of evaluating according to above-mentioned evaluation method.

Table 1

* 1, be the amount (mass parts) of the fluorochemicals of total amount 100 mass parts (solid constituent) with respect to adhesive resin (also comprising these materials while using fluorochemical monomer and fluoropolymer) and particulate.Here, solid constituent does not comprise polymerization initiator.

Table 2

* 1, be the amount (mass parts) of the fluorochemicals of the total amount of the adhesive resin with respect to 100 mass parts (solid constituent) (also comprising these compositions while using fluorochemical monomer and fluoropolymer) and particulate.At this, solid constituent does not comprise polymerization initiator.

The antireflection film of embodiment 1～5 gained, is excellence in whole evaluations, has excellent preventing reflection characteristic, has excellent mar resistance and soil resistance and without albefaction, known for having the surperficial film of uniformity from the 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 thering is the surperficial film of uniformity, can confirm that stain-proofing layer is in the mode of whole on coating low-index layer, uniformity ground forms.

Adhesive resin is replaced with to the embodiment 6 of DPHA from PETA, obtain roughly good physical property, yet though be roughly uniformity of coated face, have a little coarsely, and mar resistance declines a little.In addition, DPHA is replaced with to trimethylolpropane triacrylate (TMPTA) and tetramethylol methane tetraacrylate (PETTA), while making antireflection film, confirmation can obtain the result almost identical with embodiment 6.In the many embodiment 7 of the content of fluorochemicals, obtain roughly good physical property, yet though be roughly uniformity of surface state, have some coarsely, and mar resistance declines a little.Glycol ethers as solvent is replaced with in the embodiment 8 of toluene, infer the dispersiveness of particulate is had to some impacts, although mar resistance has some decline, obtain roughly good result.According to result, can confirm ketone, glycol ethers good as solvent result of use.In addition, the embodiment 9 that the material that patent documentation 2 is used is used as fluorochemicals, though obtain at stain-proofing layer without island structure, without the good sample of slight albefaction, the flatness of coated surface is poor and confirm slight deformation.Can confirm that thus fluorochemicals preferably has silane unit.

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, also insufficient aspect soil resistance, also confirm albefaction.In addition, landing angle is 33 ° can not be called the surface with uniformity, from the observations by atomic force microscope, confirms island structure.Can think that this island structure is because fluorine containing silane compound is few, completely the outmost surface of coating low-index layer, cannot form the stain-proofing layer of uniformity, thereby occur, can think that this is the main cause that becomes slight albefaction.Excessively comprise in the comparative example 2 of fluorochemicals, in excessive being separated of the whole generation of low-index layer, the surface integral of low-index layer is coarse significantly, does not form the stain-proofing layer of uniformity.Can thinking this, coarse to be that excessive fluorochemicals be take the teat of the particulate in low-index layer concavo-convex as opportunity produces, and it is coarse that result occurs at the surface integral of layer.And because the amount of the fluorochemicals that average surface roughness is large, stain-proofing layer is contained is many, it is soft that this stain-proofing layer can become, and the in the situation that of doing wiping, will cause scar when evaluating soil resistance.In addition, do not comprise fluorochemicals, fluorine atom/carbon atomic ratio is less than in 0.6 comparative example 3, although obtain the surface of uniformity, because the amount of fluorine is few, soil resistance is also insufficient.Comparative example 4 is the examples that do not use particulate, because the intermiscibility of adhesive resin and fluorochemicals is poor, causes the integral body of filming to bleach when dried coating film, cannot evaluate.According to such result, known in order to keep balance between the poor fluorochemicals of adhesive resin and intermiscibility, reach the formation of final purpose, the effect of particulate is indispensable.In addition, by evaporation, form in the comparative example 5 of stain-proofing layer, soil resistance and surface state are roughly good, but owing to not having to occur as antifouling reactive functional groups in mutually of the present invention and low-refraction some reactive functional groups in mutually reacts curing, a little less than stain-proofing layer after solidifying and the adaptation of low-index layer, mar resistance variation.

In industry, utilize possibility

According to the present invention, can easily manufacture and there is excellent preventing reflection characteristic, there is excellent mar resistance and soil resistance, and suppress the antireflection film of the generation of the slight albefaction never bothered about so far.The antireflection film of gained is applicable to being arranged at polarization plates, image display device.

Claims

1. the manufacture method of an 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/carbon atomic ratio of measuring 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 Ra' of this stain-proofing layer is below 10nm, wherein

Operation (1) thus be on transparent base, to be coated with low-index layer to form with composition and form the operation of filming, described low-index layer formation at least contains fluorochemicals, particulate and adhesive resin with composition;

Operation (2) is this to be filmed be separated into the operation of low-refraction phase and antifouling phase;

Operation (3) is heating this low-refraction phase and this antifouling phase, or to the antifouling ionizing ray that irradiates mutually of this low-refraction phase and this, thereby the operation of the stain-proofing layer of whole of formation low-index layer and this low-index layer of coating.

2. the manufacture method of antireflection film as claimed in claim 1, wherein, fluorochemicals is the material that contains the silane unit that has reactive silane unit and have holo-fluorine polyester.

3. the manufacture method of antireflection film as claimed in claim 2, wherein, has reactive silane unit and has the silane unit of holo-fluorine polyester, has respectively siloxane backbone.

4. the manufacture method of antireflection film as claimed in claim 2 or claim 3, wherein, reactive group is at least one being selected from (methyl) acryloyl group and vinyl.

5. the manufacture method of the antireflection film as described in any one in claim 1～4, wherein, the weight-average molecular weight of fluorochemicals is more than 5000.

6. the manufacture method of the antireflection film as described in any one in claim 1～5, wherein, particulate is silicon dioxide microparticle.

7. the manufacture method of the antireflection film as described in any one in claim 1～6, wherein, particulate comprises the particulate with space.

8. the manufacture method of the antireflection film as described in any one in claim 1～7, wherein, particulate is surface treated particulate.

9. the manufacture method of the antireflection film as described in any one in claim 1～8, 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 (methyl) acrylate that 3 officials can be above.

11. 1 kinds of antireflection films, it is to manufacture by the manufacture method of the antireflection film described in any one in claim 1～10.

12. 1 kinds of polarization plates, it is at least one side of polarizing coating, to have the polarization plates that antireflection film and this antireflection film are the antireflection film described in claim 11.

13. 1 kinds of image display devices, its outmost surface at display has antireflection film or polarization plates, and described polarization plates is at least one side of polarizing coating, to have the polarization plates of antireflection film, and described antireflection film is the antireflection film described in claim 11.