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CN104267450A - Anti-glare Film, Manufacturing Method Of Same, Polarizing Plate And Image Display Device - Google Patents

Anti-glare Film, Manufacturing Method Of Same, Polarizing Plate And Image Display Device Download PDF

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Publication number
CN104267450A
CN104267450A CN201410452995.5A CN201410452995A CN104267450A CN 104267450 A CN104267450 A CN 104267450A CN 201410452995 A CN201410452995 A CN 201410452995A CN 104267450 A CN104267450 A CN 104267450A
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China
Prior art keywords
mentioned
glare film
diffusing layer
fine particles
organic fine
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CN201410452995.5A
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CN104267450B (en
Inventor
儿玉崇
本田诚
铃木裕子
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

Disclosed is an anti-glare film having excellent shock-durability, and that suitably suppresses generation of a crack even when applied in a sheet-shaped display. The invention also provides a polarizing plate and an image display device. The anti-glare film includes a light-transmitting substrate, and a diffusion layer formed on at least one surface of the light-transmitting substrate, wherein the diffusion layer is composed of a film formed by coating and drying on at least one surface of the light-transmitting substrate a coating liquid containing a radiation-curing type binder including as an essential component a layered inorganic compound, an organic fine particle (A), and a (meth) acrylate monomer, and curing the film. The radiation-curing type binder contains (methyl) acrylate monomer as a necessary component and the layered inorganic compound is contained in a randomly oriented state. The average particle diameter of the layered inorganic compound is 0.3 micrometer to 5 micrometers.

Description

The manufacture method of anti-glare film, anti-glare film, polaroid and image display device
The application is divisional application, and the China national application number of its original application is 201180016716.5, and the applying date is on March 25th, 2011, and denomination of invention is " manufacture method of anti-glare film, anti-glare film, polaroid and image display device ".
Technical field
The present invention relates to anti-glare film, the manufacture method of this anti-glare film, polaroid and image display device.
Background technology
In the image display devices such as CRT display (CRT), LCDs (LCD), plasma display panel (PDP) (PDP), electroluminescent display panel (ELD), Electronic Paper, usually arrange for preventing the optical laminate reflected in outmost surface.Such antireflection optical laminate suppresses mirroring or reducing reflectivity of image by the diffusion of light or interference.
As one of antireflection optical laminate, there will be a known the anti-glare film defining the antiglare layer with concaveconvex shape on the surface of transparent base material.This anti-glare film utilizes the concaveconvex shape on surface and makes exterior light diffusion, thus can prevent the reduction of observability.
As existing anti-glare film, such as, there will be a known and comprise the resin of the fillers such as silicon dioxide (silica) to form the anti-glare film (such as, see patent documentation 1,2) of antiglare layer in the coating of the surface of transparent base film.
These anti-glare films have with Types Below: be added in resin by aggregation particle or inorganic and/or organic filler, form the type of concaveconvex shape on layer surface; Or the irregular film of layer surface tool is carried out lamination, carry out the type that transfer printing goes out concaveconvex shape; Or utilize two or more polymkeric substance etc. to form the compound compatibility each other of bonding agent, make it be separated, thus form the type of concaveconvex shape; Etc..
For existing like this anti-glare film, no matter be which kind of type, will by the surface configuration of antiglare layer be used for obtain light diffusion and anti-dazzle effect, all need to increase concaveconvex shape to improve anti-glare, if but concavo-convex increase, then the haze value (turbidity value) of film rises, and can fade, and has the problem reduced through visibility therewith together.
In addition, in the anti-glare film of existing type, also can be called as the radiance of the flicker of so-called face dazzle (face ギ ラ) on film surface, the problem that the observability with display frame reduces.
But in recent years, although the high-precision refinement of LCDs develops gradually, if be applicable in the LCDs of fine by existing anti-glare film, then the generation of face dazzle can become more serious problem.
In addition, as forming the adhesive resin of antiglare layer, use and carry out to ultraviolet-curing adhesive resin the material that Ultraviolet radiation makes it to solidify, such antiglare layer is comparatively hard, but shock-resistant weak.
In the bonding process of polaroid manufacturing process or polaroid and liquid crystal cell, sometimes reduce the radius-of-curvature of anti-glare film, apply locally to increase the weight of, but use possess the above-mentioned harder but anti-glare film of shock-resistant weak antiglare layer time, then there is the problem that antiglare layer cracks.Further, as LCDs, require higher loss prevention trauma, due to the local fine crack producing damage owing to increasing the weight of may be there is, thus require that anti-glare film has crackle patience, namely has resistance to impact.
Further, in the anti-glare film manufactured in the polymerization shrinkage by ultraviolet curable resin, also have and curling such problem can occur.
The anti-dazzle material resin bead of swelling in a solvent more than 70% and adhesive resin mixed is described in patent documentation 3.
Such carry out in the anti-glare film of the antiglare layer of swelling resin bead in a solvent in advance by using possessing, the raising of the interface adaptation of resin bead and adhesive resin can be expected, the raising of the resistance to impact of antiglare layer can be sought, thus expect to be suitable for paramount becoming more meticulous in display screen.
But, possessing by using in the anti-glare film of the antiglare layer of having carried out swelling resin bead in advance in a solvent, the raising that there occurs the interface adaptation of swelling resin bead and adhesive resin in antiglare layer only depends on the anchor effect (ア ン カ ー effect) produced at this interface, and therefore adaptation etc. exist the leeway of improving further.
Therefore, for existing anti-glare film, the resistance to impact as antiglare layer entirety is insufficient, in above-mentioned polaroid manufacturing process etc. or when being applicable to LCDs, not can fully prevent from cracking in antiglare layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-18706 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-20103 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-281476 publication
Summary of the invention
Invent problem to be solved
In view of above-mentioned present situation, the object of the present invention is to provide without face dazzle, there is the resistance to impact of excellence, the anti-glare film of crackle and curling generation can be suppressed well; The manufacture method of this anti-glare film; Apply polaroid and the image display device of this anti-glare film.
For solving the means of problem
Anti-glare film of the present invention is the anti-glare film with Mght-transmitting base material and diffusing layer, this diffusing layer is formed at least one face of this Mght-transmitting base material, surface has concaveconvex shape, the feature of this anti-glare film is, above-mentioned diffusing layer is that the coating solution containing layered inorganic compound, organic fine particles (A) and radiation curable bonding agent is carried out drying to form film and to make this curing of coating at least one face of above-mentioned Mght-transmitting base material, and described radiation curable bonding agent comprises (methyl) acrylate monomer as neccessary composition; The content of the above-mentioned layered inorganic compound in above-mentioned coating fluid is 2 mass parts ~ 40 mass parts relative to above-mentioned radiation curable bonding agent 100 mass parts; Above-mentioned layered inorganic compound contains with random orientation state in above-mentioned diffusing layer.
In anti-glare film of the present invention, above-mentioned layered inorganic compound is preferably talcum.
In addition, the solvent of above-mentioned coating fluid preferably containing swelling organic fine particles (A).
In addition, preferred above-mentioned coating fluid is further containing particulate (B), and the organic fine particles (A) in diffusing layer has the infiltration layer that is impregnated with radiation curable bonding agent and has the mean grain size larger than the mean grain size of the particulate (B) in above-mentioned diffusing layer.
Above-mentioned particulate (B) is preferably the particulate of lipophilicity higher than organic fine particles (A).
In addition, the specific refractivity of the refractive index of above-mentioned radiation curable bonding agent and the specific refractivity of organic fine particles (A) and the refractive index of radiation curable bonding agent and particulate (B) is being set to Δ respectively aand Δ btime, preferred above-mentioned Δ aand Δ bmeet following formula (1).
|Δ A|<|Δ B| (1)
In addition, the invention still further relates to the manufacture method of anti-glare film, it is the manufacture method of the anti-glare film with Mght-transmitting base material and diffusing layer, this diffusing layer is formed at least one face of this Mght-transmitting base material, surface has concaveconvex shape, it is characterized in that, the method has following operation: will containing layered inorganic compound, the coating solution of organic fine particles (A) and radiation curable bonding agent is at least one face of above-mentioned Mght-transmitting base material, carry out drying to form film, make this curing of coating and form described diffusing layer, wherein said radiation curable bonding agent comprises (methyl) acrylate monomer as neccessary composition, above-mentioned layered inorganic compound in above-mentioned diffusing layer contains with random orientation state.
In addition, the invention still further relates to polaroid, it is the polaroid possessing polarization element, and the feature of this polaroid is, possesses anti-glare film of the present invention on the surface of above-mentioned polarization element.
In addition, the invention still further relates to image display device, the feature of this image display device is, it possesses anti-glare film of the present invention or polaroid of the present invention in outmost surface.
Below describe the present invention in detail.
Anti-glare film of the present invention has Mght-transmitting base material and diffusing layer, and this diffusing layer is formed at least one face of this Mght-transmitting base material, surface has concaveconvex shape.
Above-mentioned Mght-transmitting base material preferably possesses flatness, thermotolerance, mechanical strength.As the concrete example of the material of the above-mentioned Mght-transmitting base material of formation, can enumerate: polyester (polyethylene terephthalate, PEN), cellulose triacetate, cellulose diacetate, cellulose acetate-butyrate, polyamide, polyimide, polyethersulfone, polysulfones, polypropylene, polymethylpentene, Polyvinylchloride, Pioloform, polyvinyl acetal, polyetherketone, polymethylmethacrylate, polycarbonate, or polyurethane, the thermoplastic resins such as cyclopolyolefin, preferably enumerate polyester (polyethylene terephthalate, PEN), cellulose triacetate.
Above-mentioned Mght-transmitting base material preferably uses with the above-mentioned form being imbued with the membranous body of flexibility, corresponding to the use-pattern requiring curability, also can use the plate of these thermoplastic resins or also can use the tabular body of glass plate etc.
As the thickness of above-mentioned Mght-transmitting base material, be preferably 20 μm ~ 300 μm, the preferred upper limit is 200 μm, and lower limit is 30 μm.When Mght-transmitting base material is tabular body, also can for being greater than the thickness of these thickness.
In addition, for above-mentioned Mght-transmitting base material, when forming diffusing layer thereon, in order to improve cementability, except the physical treatments such as Corona discharge Treatment, Cement Composite Treated by Plasma, saponification process, oxidation processes, also can be coated with tackifier in advance or be called as the coating of priming paint.
In anti-glare film of the present invention, above-mentioned diffusing layer is using containing layered inorganic compound, organic fine particles (A) and comprise the coating solution of (methyl) acrylate monomer as the radiation curable bonding agent of neccessary composition at least one face of above-mentioned Mght-transmitting base material, carry out drying to form film, and make this curing of coating.In addition, in the present invention, unless otherwise specified, above-mentioned diffusing layer represents the film layer of solidification.
Be not particularly limited as above-mentioned layered inorganic compound, such as polynite, beidellite, nontronite, saponite, hectorite, sauconite, humite, vermiculite, halloysite, smalite, halloysite, dickite, talcum, pyrophyllite, mica, emerylite, white mica, phlogopite, tetrasiuicic fluoromica (テ ト ラ シ リ リ ッ Network マ イ カ), taincolite, antigorite, chlorite, cookeite, nepouite etc. can be enumerated.These layered inorganic compounds can be natural goods, also can be complex.In addition, above-mentioned layered inorganic compound can be applied in organic surface treatment.
The particle diameter of these layered inorganic compounds represents with the mean grain size D50 (the intermediate value footpath of domain size distribution) based on laser diffraction and scattering formula particle size distribution method.Preferred particle size range is 0.1 μm ~ 9 μm, is more preferably 0.3 μm ~ 5 μm.
For these layered inorganic compounds, when utilizing SEM etc. to observe the cross section of the anti-glare film of reality, be that the form of the plate-like particles of 0.3 μm ~ about 5 μm exists with major diameter.In order to solve problem of the present invention, if above-mentioned particle diameter is too small also cannot give play to effect, if excessive, sometimes also impact can be had on the transparency of anti-glare film entirety.In at the particle diameter being undertaken by SEM can measuring in the result of cross-section, preferred scope to be major diameter the be plate-like particles of 0.3 μm ~ about 2.5 μm.In addition, in the mensuration of major diameter, what take is the mean value of 10 major diameters of plate-like particles seen by the SEM cross-section.
In anti-glare film of the present invention, above-mentioned layered inorganic compound contains with random orientation state in above-mentioned diffusing layer.In addition, what is called refers at random, in the cross section of above-mentioned diffusing layer, in the region that the thickness at this diffusing layer and the vertical direction (10 μm) relative to this thickness direction are formed, the major diameter of layered inorganic compound or the extended line of major diameter are not the states be parallel to each other.Now, preferably parallel be less than 3 one-tenth, be more preferably less than 2 one-tenth.
By making above-mentioned layered inorganic compound contain with random orientation state in diffusing layer, even if when above-mentioned diffusing layer applies stress because distortion waits from various direction, also can prevent it from becoming the starting point of crackle.In addition, even if carry out Ultraviolet radiation when the making of this diffusing layer, the above-mentioned layered inorganic compound contained with random orientation state has relaxed the infringement caused by Ultraviolet radiation, also can suitably prevent from producing in manufactured anti-glare film curling further.
By inference, its reason is, above-mentioned layered inorganic compound has the sandwich construction that interlayer is combined into through Van der Waals force, because the adhesion of this interlayer is weak, impact if thus apply, then this interlayer misplaces, thus the shear stress that Absorbable rod applies, be easier to thus absorb and impact.In addition, by making such layered inorganic compound contain with random orientation state in above-mentioned diffusing layer, for the stress that all directions from diffusing layer apply, above-mentioned impact absorbing effect can have been given play to.
That is, in anti-glare film of the present invention, by making above-mentioned layered inorganic compound contain with random orientation state in diffusing layer, resistance to impact can be made very excellent.
As such layered inorganic compound, the mineral compound wherein preferably containing Si, Al, Mg, O element, as the compound containing such element, talcum is applicable.For talcum, for the reason of its physical property and crystalline texture, it to be easy in the radiation curable bonding agent of above-mentioned coating fluid endless dispersion multi-directionly and to exist, and very compatibly can obtain the effect of the anti-glare film of the invention described above.
Further, such as, contain particulate described later (B) at above-mentioned diffusing layer, above-mentioned organic fine particles (A) be cross-linked acrylic acid pearl, above-mentioned particulate (B) for polystyrene, if above-mentioned layered inorganic compound is talcum, then suitably can control the gathering of above-mentioned organic fine particles (A) and particulate (B).Its result, the anti-glare film obtained can realize high-caliber anti-glare, preventing sheding tintability, anti-dazzle.
This is above-mentioned talcum is by inference that the material that lipophilicity is high creates impact.Namely, organic fine particles (A) (crosslinked acrylic resin) has hydrophilic character, particulate (B) (polystyrene) has oil loving character, infers that the gathering of talcum to two particulates that lipophilicity is high adjusts.
In addition, the form as above-mentioned talcum is layer structure, is also included within during cross sectional microscopy is observed and appears as needle-like or fibrous structure.
In above-mentioned coating fluid, the content of above-mentioned layered inorganic compound is 2 mass parts ~ 40 mass parts relative to above-mentioned radiation curable bonding agent 100 mass parts.If be less than 2 mass parts, then the resistance to impact of anti-glare film of the present invention is insufficient; If more than 40 mass parts, then the viscosity of above-mentioned diffusing layer coating fluid increases, and possibly cannot be coated with or may uncontrollable film coated surface concavo-convex.In addition, when the content of above-mentioned layered inorganic compound exceeds above-mentioned scope, if addition is very few, then can not exist with random orientation state well in whole diffusing layer, thus suitably cannot regulate the gathering of the organic fine particles existed in the lump (A), thus meeting generating plane dazzle; Otherwise, if excessive existence, then fully cannot prevent the reduction of contrast.The preferred lower limit of the content of above-mentioned layered inorganic compound is 2 mass parts, preferred upper limit is 30 mass parts.By being in this scope, can give play to resistance to impact effect better, also easier control surface is concavo-convex simultaneously.
Above-mentioned organic fine particles (A) be mainly formed on the surface of above-mentioned diffusing layer concavo-convex with the particulate making surface diffusion function manifest, as the material forming such organic fine particles (A), such as organic siliconresin, polyester, polystyrene, acryl resin, polyacrylic acid-styrene copolymerized resin, olefin resin etc. can be enumerated.Wherein be suitable for using acryl resin, further the preferred crosslinked acrylic resin changing the type of crosslinking degree making cross-linking density raising etc. when manufacturing particulate.In addition, in this manual, " resin " is the concept also comprising the reactive or non-reacted resinous principle such as polymkeric substance, monomer, oligomer.
In addition, in order to suppress the face dazzle of anti-glare film of the present invention, more preferably above-mentioned organic fine particles (A) has refractive indices relative to radiation curable bonding agent described later a, make above-mentioned diffusing layer have internal diffusion function.
Specifically, when not using particulate described later (B), preferred above-mentioned refractive indices abe less than 0.1; When particulate (B) that state after a procedure, preferred above-mentioned refractive indices abe less than 0.04.
As above-mentioned crosslinked acrylic resin, such as use the crosslinking chemicals such as polymerization initiator and Ethylene glycol dimethacrylate such as persulfuric acid, be polymerized acrylic monomers such as such as acrylic acid and acrylate, methacrylic acid and methacrylate, acrylamide, vinyl cyanide by suspension polymerization etc., the homopolymer obtained or multipolymer are applicable.
Be monomer as aforesaid propylene acid, use methyl methacrylate and the crosslinked acrylic resin that obtains is particularly suitable for.
As above-mentioned organic fine particles (A) mean grain size in film, the scope of such as 0.5 μm ~ 15.0 μm is applicable.The scope of particularly 1.0 μm ~ 10.0 μm is more applicable to.If above-mentioned mean grain size is less than 0.5 μm, then the anti-glare of anti-glare film of the present invention and anti-dazzle sometimes insufficient; If more than 15.0 μm, then the image outline producing the display screen of the anti-glare film of the application of the invention such as to thicken at the harsh feeling (ガ サ Star キ) be short of in image compactness, and image quality may reduce.
In addition, above-mentioned mean grain size refers to, if each particle contained in diffusing layer is the particle that shape is single, is then the arithmetic mean of its particle diameter; If have the particle of the unsetting type of wide size-grade distribution, then for be there is the particle diameter of maximum particles by particle size distribution.In addition, above-mentioned particle diameter can be measured by coulter counter method etc. when being only the state of particulate.But, except the method, as the fine grain measurement method in cured film, SEM observation can also be carried out to the cross section of the anti-glare film of actual fabrication and measure based on its photograph taking, infiltration type optical microscope maybe can be utilized to observe anti-glare film surface, thus measuring.
In anti-glare film of the present invention, in above-mentioned diffusing layer, above-mentioned organic fine particles (A) preferably has the infiltration layer being impregnated with radiation curable bonding agent described later.In addition, in the following description, the organic fine particles (A) be formed in organic fine particles (A), the i.e. diffusing layer of above-mentioned infiltration layer is also referred to as " organic fine particles (A2) ".
By having above-mentioned infiltration layer, above-mentioned organic fine particles (A2) is very excellent with the adaptation of the solidfied material (hereinafter also referred to adhesive resin) of the radiation curable bonding agent of diffusing layer.In addition, because the above-mentioned infiltration layer in organic fine particles (A2) is formed with the state being mixed with radiation curable bonding agent, therefore, the refractive index of above-mentioned infiltration layer is the refractive index between the refractive index of radiation curable bonding agent and the refractive index of organic fine particles (A), thus can suitably reduce above-mentioned diffusing layer through the reflection of light on the interface of above-mentioned organic fine particles (A2) (infiltration layer) and adhesive resin.In addition, meanwhile, above-mentioned infiltration layer is the thickness of appropriateness, and the central part of organic fine particles (A2) maintains the refractive index of the organic fine particles (A) at initial stage, and thus internal diffusion can not reduce, and can suitably prevent face dazzle.
Further, as described later, above-mentioned infiltration layer is that above-mentioned radiation curable bonding agent and/or solvent make organic fine particles (A) that swelling and layer that is that suitably formed occur, and thus above-mentioned organic fine particles (A2) is the particulate being extremely imbued with flexibility.Therefore, on the surface of above-mentioned diffusing layer, although the position corresponding with organic fine particles (A2) in this diffusing layer forms protuberance, the shape of this protuberance can be made mild.In addition, about this point, be described in further detail below.
Above-mentioned infiltration layer is that above-mentioned radiation curable bonding agent carries out infiltrating from the outside surface of the organic fine particles (A2) above-mentioned diffusing layer towards its center and the layer formed.In addition, the layer that above-mentioned infiltration layer is low molecular weight compositions in radiation curable bonding agent and monomer infiltration and is formed, is difficult to infiltration as the polymkeric substance of the radiation curable bonding agent of high molecular weight components and polymkeric substance or oligomer.But, even oligomer or polymkeric substance, be also the smaller material of molecular weight sometimes, together infiltrate when monomer infiltrates.
For above-mentioned infiltration layer, such as, SEM etc. can be utilized to observe the cross section of above-mentioned diffusing layer, be judged by the cross section observing organic fine particles (A2) wherein.As the method that it is detailed, diffusing layer is cut off at thickness direction, to 50,000 times, SEM observation is carried out with multiple 3,000 times to the cross section at least containing the organic fine particles (A2) of more than 1, the part in organic fine particles (A2) is infiltrated up at radiation curable bonding agent, observe organic fine particles (A2) more clear with the border of the radiation curable bonding agent of surrounding, and radiation curable bonding agent is the part of maximum infiltration in organic fine particles (A2), the mensuration such as SEM photo are utilized to the thickness of 2 of this part, measure equally amounting to 5 organic fine particles (A2), calculate the mean value of 10 measurement results.Suppose when except organic fine particles (A2) also containing other particulate etc., the thickness of infiltration layer in this particulate can be measured as described above.
In addition, the radiation curable bonding agent infiltrated in above-mentioned infiltration layer can be that whole constituent infiltrates, also can be constituent with a portion of infiltration.
In addition, the average thickness of above-mentioned infiltration layer is preferably 0.01 μm ~ 1.0 μm.If be less than 0.01 μm, then sometimes fully cannot obtain the effect obtained by forming above-mentioned infiltration layer; If more than 1.0 μm, then the internal diffusion function of organic fine particles (A2) cannot give full play to, and possibly fully cannot obtain the effect preventing face dazzle.More preferably the lower limit of the average thickness of above-mentioned infiltration layer is 0.1 μm, more preferably the upper limit be 0.8 μm.By within the scope of this, above-mentioned effect can be given play to further.In addition, from the viewpoint of guaranteeing internal diffusion function, prevent face dazzle, the footpath not forming the central part of infiltration layer of organic fine particles (A2) is preferably more than the wavelength of light.
In addition, the average thickness of above-mentioned infiltration layer refers to, the mean value of the infiltration layer thickness in the cross section of the organic fine particles (A) utilizing the section S EM photo of anti-glare film to observe.
Herein, organic fine particles has crosslinked structure usually, according to the difference of this crosslinking degree, the degree of swelling that above-mentioned radiation curable bonding agent and/or solvent cause is different, usually, if the degree of crosslinking of organic fine particles uprises, swellbility reduces, if degree of crosslinking is low, swellbility uprises.Therefore, such as, when the material of the above-mentioned organic fine particles of formation (A2) is above-mentioned crosslinked acrylic resin, by suitably adjusting the crosslinking degree of this crosslinked acrylic resin, can by the THICKNESS CONTROL of above-mentioned infiltration layer in desired scope.In addition, from the aspect of antireflection and anti-dazzle, above-mentioned organic fine particles (A2) more preferably central part degree of crosslinking uprises, most preferably above-mentioned organic fine particles (A2) with infiltration layer thickness be in a ratio of inner side side have be not infiltration property degree of crosslinking and surface-crosslinked degree is low.
In addition, the mean grain size of above-mentioned organic fine particles (A) is being set to D a1, the mean grain size of the organic fine particles (A2) in diffusing layer is set to D awhen 2, this D a1, D a2 preferably meet following formula (2).
0.01μm<D A2-D A1<1.0μm (2)
In above-mentioned formula (2), if " D a2-D a1 " be less than 0.01 μm, then the thickness of above-mentioned infiltration layer is excessively thin, sometimes cannot obtain the effect obtained by forming above-mentioned infiltration layer.If " D a2-D a1 " be more than 1.0 μm, then internal diffusion function cannot give full play to, and sometimes fully cannot obtain the effect preventing face dazzle.
Above-mentioned " D a2-D a1 " preferred lower limit is 0.1 μm, the preferred upper limit is 0.5 μm.By making " D a2-D a1 " be in this scope, above-mentioned effect can have been given play to further.
In addition, preferred above-mentioned organic fine particles (A) is not assembled at the thickness direction of this diffusing layer (longitudinal direction) in above-mentioned diffusing layer.If the organic fine particles (A) in above-mentioned diffusing layer is assembled aheap at the thickness direction of this diffusing layer, diffusing layer surface then in the position corresponding with the organic fine particles (A) assembled can form large protuberance, and anti-glare film of the present invention fades or face dazzle sometimes.In addition, such as by suitably can prevent the gathering of the organic fine particles (A) in above-mentioned diffusing layer containing above-mentioned layered inorganic compound, when using talcum as this layered inorganic compound, suitably can prevent the gathering of above-mentioned organic fine particles (A) especially.In addition, for the gathering of above-mentioned organic fine particles (A), with it compared with the gathering of longitudinal direction, its vertical direction at the thickness direction of diffusing layer (transverse direction) occurs to assemble, lessly cause the problems referred to above, if but aggregation block is excessive, then also can produce same problem, thus be suitable for adding stratiform acid/mineral compounds in the same manner as longitudinal situation of assembling.
In addition, in anti-glare film of the present invention, above-mentioned organic fine particles (A) has infiltration layer in diffusing layer, as such organic fine particles (A), such as utilize the coating fluid employing the different organic fine particles of degree of crosslinking to make anti-glare film in advance, select the organic fine particles consistent with preferred infiltration degree to carry out using.This organic fine particles selected in, composition, all resins compound namely contained by base binder, various adjuvant, solvent etc. beyond the organic fine particles forming diffusing layer can have an impact, and thus preferred degree of crosslinking cannot treat different things as the same.Thus, in the base composition that it is selected constantly, add the particulate of various degree of crosslinking in advance, solidification making diffusing layer, utilize said method to measure the thickness of infiltration layer, thus select particle.
In addition, the content as the organic fine particles (A) in above-mentioned coating fluid is not particularly limited, and relative to radiation curable bonding agent 100 mass parts described later, is preferably 0.5 mass parts ~ 30 mass parts.If be less than 0.5 mass parts, then cannot form sufficient concaveconvex shape on the surface of diffusing layer, the anti-dazzle performance of anti-glare film of the present invention may be insufficient.On the other hand, if more than 30 mass parts, be then easy in above-mentioned coating fluid produce organic fine particles (A) gathering to each other, in above-mentioned diffusing layer can above-mentioned vertical or horizontal on produce assemble, large protuberance can be formed on the surface of diffusing layer, fade sometimes or face dazzle.The preferred lower limit of the content of above-mentioned organic fine particles (A) is 1.0 mass parts, the preferred upper limit is 20 mass parts.By within the scope of this, above-mentioned effect can be made more reliable.
Above-mentioned coating fluid is preferably further containing particulate (B).Above-mentioned particulate (B) is mainly the particulate for obtaining internal diffusion, by containing above-mentioned particulate (B), can more suitably prevent in formed diffusing layer generating plane dazzle.Specifically, the refractive indices of above-mentioned particulate (B) and radiation curable bonding agent bbe preferably greater than the refractive indices of above-mentioned organic fine particles (A) and radiation curable bonding agent a, be less than 0.2.If refractive indices bbe greater than 0.2, then internal diffusion is excessively strong, may produce and fades thus contrast is reduced; If refractive indices bbe less than above-mentioned refractive indices a, then internal diffusion is excessively weak, and the suppression of face dazzle may be insufficient.In order to obtain above-mentioned effect, above-mentioned refractive indices bbe more preferably more than 0.01 and less than 0.1.
As such particulate (B), be preferably not by the radiation curable bonding agent in above-mentioned coating fluid and/or the swelling particle of solvent.If this is because, particulate (B) has infiltration layer, then particulate (B) can reduce with the diffusion of the interface of bonding agent.
Herein, " not by ... swelling particle " comprises completely not by the situation of above-mentioned radiation curable bonding agent and/or solvent swell, comprises in addition slightly by swelling situation.Above-mentioned " slightly by swelling situation " refers to, in above-mentioned diffusing layer, above-mentioned particulate (B) is formed with the infiltration layer same with above-mentioned organic fine particles (A2), but the average thickness of this infiltration layer is less than the infiltration layer of above-mentioned organic fine particles (A) and is less than the situation of 0.1 μm.
The judgement of infiltration layer whether is formed with such as by utilizing the cross section of microscope (SEM etc.) to the particulate (B) of above-mentioned diffusing layer to carry out observation to carry out about the particulate (B) in above-mentioned diffusing layer.
In addition, in the following description, the particulate (B) in above-mentioned diffusing layer is called " particulate (B2) ".
As above-mentioned not by the particulate (B) of radiation curable bonding agent and/or solvent swell, the inorganic particles such as such as silicon dioxide microparticle can be enumerated; The particulate etc. that improve degree of crosslinking in the organic fine particles such as polystyrene, melamine resin, polyester, acryl resin, olefin resin or their multipolymer; Preferably be easy to the organic fine particles of the adjustment carrying out refractive index and particle diameter.These particulates (B) can be used alone, and also can two or more share.
Wherein, high from refractive index, be easy to arrange and the refringence (refractive index of usual radiation curable bonding agent is about 1.48 ~ 1.54) of bonding agent, the aspect easily obtaining internal diffusion, be suitable for using ps particle and/or acrylic-styrene copolymer particulate.In addition, the situation being organic granular with particulate (B) is below described.
Herein, for the organic fine particles utilizing acryl resin, styrene resin, when utilizing usually known manufacture method to manufacture, acrylicstyrene copolymer resins is all used as material, or in core-shell type particulate, have the ps particle employing the particulate formed by acryl resin in core or the polyacrylic acid particulate employing the particulate formed by styrene resin in contrast to this in core.In this manual, about the difference of acrylic particles, styrene particulate, acrylicstyrene copolymerized particle, by the characteristic that has particulate and which resin is more close judges.Such as, if the refractive index of particulate is less than 1.50, then desirable its is acrylic particles; If more than 1.50 and be less than 1.59, then desirable its is acrylic-styrene copolymer particulate; If more than 1.59, then desirable its is styrene particulate.
Mean grain size as above-mentioned particulate (B) is not particularly limited, and can be equal particle diameter with the mean grain size of above-mentioned organic fine particles (A).But, above-mentioned organic fine particles (A) is by being formed infiltration layer by above-mentioned radiation curable bonding agent and/or solvent swell when, in order to fully obtain the effect of adding above-mentioned particulate (B), the mean grain size of preferred above-mentioned organic fine particles (A) is greater than the mean grain size of the particulate (B) in diffusing layer, further, the mean grain size of the mean grain size of above-mentioned organic fine particles (A) and particulate (B) and the organic fine particles (A) of materials behavior and particulate (B) is being set to D respectively a1 and D b1, the mean grain size of the organic fine particles (A2) in diffusing layer and particulate (B2) is set to D respectively a2 and D bwhen 2, above-mentioned D a1, D b1, D a2 and D b2 preferably meet following formula (3).
1.0μm>D A2-D A1>D B2-D B1≧0(3)
By meeting above-mentioned formula (3), the concaveconvex shape on diffusing layer surface is level and smooth, suppress the change etc. because of the infiltrations such as bonding agent particle refractive index caused in the particle contributing to internal diffusion simultaneously, therefore be easy to maintain internal diffusion, and particle surface is reduced with the refringence of bonding agent by infiltration, thus inhibitory reflex, therefore, it is possible to make a fade-proof and anti-dazzle of anti-glare film of the present invention more reliable.
In addition, the refractive indices of the particulate (B) in diffusing layer and radiation curable bonding agent b2 large when (such as there is Δ b2 when being the refringence of more than 0.02), more preferably above-mentioned D a2 are greater than above-mentioned D b2.This is because, be less than organic fine particles (A) by the mean grain size of the particulate (B) making internal diffusion large, diffusing layer inside can be distributed in a wide range, alleviate the generation of face dazzle in anti-glare film of the present invention or harsh feeling.
In anti-glare film of the present invention, as above-mentioned particulate (B), such as, utilize the coating fluid employing the different organic fine particles of degree of crosslinking to make antiglare film in advance, select the organic fine particles consistent with preferred infiltration degree to use.
Content as the particulate (B) in above-mentioned coating fluid is not particularly limited, and relative to radiation curable bonding agent 100 mass parts described later, is preferably 0.5 mass parts ~ 30 mass parts.If be less than 0.5 mass parts, then easy generating plane dazzle in anti-glare film of the present invention; On the other hand, if more than 30 mass parts, then the contrast employing the image displa layer of anti-glare film of the present invention reduces sometimes.The preferred lower limit of above-mentioned particulate (B) content is 1.0 mass parts, the preferred upper limit is 20 mass parts.By within the scope of this, above-mentioned effect can be made more reliable.
In anti-glare film of the present invention, as above-mentioned radiation curable bonding agent, comprise (methyl) acrylate monomer as neccessary composition.
As such radiation curable bonding agent, can enumerate the material of the swelling above-mentioned organic fine particles (A) of energy aptly, the material of preferably clear, such as, can enumerate the ionizing radiation curable resin be cured by ultraviolet or electron ray.In addition, in this instructions, " (methyl) acrylate " refers to methacrylate and acrylate.Further, in this manual, monomer refers to, makes polymer film to be solidified by ionizing ray, comprises whole molecule of the structural unit of the basic structure that can form this polymer film and has the material of unsaturated link.That is, if oligomer or prepolymer are the elementary cell of cured film, then oligomer or prepolymer is also comprised.In the present invention, above-mentioned monomer preferred molecular weight is the minor comonomer of less than 5000.
As above-mentioned (methyl) acrylate monomer, the compound that the compound etc. such as with (methyl) acrylic ester functional group has more than 1 or 2 unsaturated link can be enumerated.
As the compound with 1 unsaturated link, (methyl) ethyl acrylate, (methyl) EHA, styrene, methyl styrene, NVP etc. can be enumerated such as.As the compound with more than 2 unsaturated links, can enumerate such as: poly-hydroxymethyl-propane three (methyl) acrylate, hexanediol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, diglycol two (methyl) acrylate, polyglycol two (methyl) acrylate, Bisphenol F EO modification two (methyl) acrylate, bisphenol-A EO modification two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol five (methyl) acrylate, isocyanuric acid EO modification two (methyl) acrylate, isocyanuric acid EO modification three (methyl) acrylate, trimethylolpropane PO modification three (methyl) acrylate, trimethylolpropane EO modification three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, the resultant of reaction (poly-(methyl) acrylate ester of such as polyvalent alcohol) etc. of the polyfunctional compounds such as neopentyl glycol two (methyl) acrylate and (methyl) acrylate etc.And carbamate (methyl) acrylate or polyester (methyl) acrylate with more than 2 unsaturated links can be enumerated.
Wherein, when paying attention to the hard painting of above-mentioned diffusing layer, above-mentioned radiation curable bonding agent be preferably more than 50% (mass ratio) of whole monomer component there are 3 officials can the acrylate of above reactive group.
As above-mentioned ionizing radiation curable resin, except above-mentioned (methyl) acrylate monomer, there is the vibrin of the lower molecular weight of unsaturated double-bond, polyether resin, acryl resin, epoxy resin, carbamate resins, alkyd resin, spiral shell acetal resin, polybutadiene, polythiol-polyenoid resin etc. and also can be used as the use of above-mentioned ionizing radiation curable resin.
When above-mentioned ionizing radiation curable resin uses as ultraviolet curing resin, above-mentioned coating fluid is preferably containing Photoepolymerizationinitiater initiater.
As above-mentioned Photoepolymerizationinitiater initiater, acetophenones, benzophenone, rice Chi benzoylbenzoate (Michler's benzoyl benzoate), α-A meter Luo Ji ester (α-ア ミ ロ キ シ system エ ス テ Le), thioxanthene ketone, phenylpropyl alcohol ketone, benzil class, benzoin class, acylphosphine oxide class can be enumerated in concrete example.And preferred photosensitizer used in combination, as its concrete example, can enumerate such as n-butylamine, triethylamine, tri-n-butyl phosphine etc.
As above-mentioned Photoepolymerizationinitiater initiater, when above-mentioned ultraviolet curing resin is the resin system with free-radical polymerised unsaturated group, be preferably used alone or as a mixture acetophenones, benzophenone, thioxanthene ketone, benzoin, benzoin methylether etc.And, when above-mentioned ultraviolet curing resin is the resin system with cationically polymerizable functional group, as above-mentioned Photoepolymerizationinitiater initiater, preferably use separately or as a mixture aromatic diazonium salt, aromatic series sulfonium salt, aromatic iodonium salts, metallocene compound, benzoin sulphonic acid ester etc.
The addition of above-mentioned Photoepolymerizationinitiater initiater is preferably 0.1 mass parts ~ 10 mass parts relative to ultraviolet curing resin 100 mass parts.
In addition, above-mentioned ionizing radiation curable resin also can share with solvent-dry type resin (thermoplastic resin etc., by means of only making the solvent added to adjust solid constituent during coating carry out the resin that drying can form overlay film) and use.In this case, above-mentioned solvent-dry type resin plays the effect of adjuvant, main use ionizing radiation curable resin.As the addition of above-mentioned solvent-dry type resin, be preferably below 40 quality % relative to the total solid composition of the resinous principle contained by above-mentioned coating fluid.
As above-mentioned solvent-dry type resin, mainly thermoplastic resin can be enumerated.As above-mentioned thermoplastic resin, utilize the material usually exemplified.By the interpolation of above-mentioned solvent-dry type resin, the paint film defect of coated face effectively can be prevented.
As the concrete example of preferred thermoplastic resin, such as phenylethylene resin series, (methyl) acrylic resin, vinyl acetate system resin, vinyl ether system resin, halogen-containing resin, ester ring type ethylene series resin, polycarbonate-based resin, polyester based resin, polyamide series resin, cellulose derivative, silicone-based resin and rubber or elastic body etc. can be enumerated.
As above-mentioned thermoplastic resin, usually preferably using is noncrystalline and the resin dissolved in organic solvent (particularly the general solvent of solubilized polymkeric substance of more than two kinds or curability compound).Particularly preferably mouldability or masking, the transparency, resin that weatherability is high, such as optimization styrene system resin, (methyl) acrylic resin, ester ring type ethylene series resin, polyester based resin, cellulose derivative (cellulose esters etc.) etc.Particularly from the aspect good with the balance of the compatibility of acrylate monomer, hardness and optical characteristics, particularly preferably (methyl) acrylic resin.
According to optimal way of the present invention, when the material of above-mentioned Mght-transmitting base material is the cellulose-based resins such as triacetyl cellulose " TAC ", as the preferred concrete example of thermoplastic resin, cellulose-based resin, such as cellulose nitrate, acetylcellulose, cellulose acetate-propionate, ethylhydroxyethylcellulose etc. can be enumerated.By using above-mentioned cellulose-based resin, adaptation and the transparency of Mght-transmitting base material and the substrate buckle layer to be formed as required can be improved.
Above-mentioned coating fluid also can contain thermoset resin further.As above-mentioned thermoset resin, such as phenol resin, carbamide resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, urethane resin, epoxy resin, amino-alkyd resin, melamine-urea cocondensation resin, silicones, polyorganosiloxane resin etc. can be enumerated.When using thermoset resin, also can share the hardening agent such as crosslinking chemical, polymerization initiator, polymerization accelerant, solvent, viscosity modifier etc. as required and use.
In anti-glare film of the present invention, the refractive index of above-mentioned radiation curable bonding agent after solidification and the specific refractivity of organic fine particles (A) and particulate (B) are set to Δ respectively aand Δ btime, preferred above-mentioned Δ aand Δ bmeet following formula (1).
|Δ A|<|Δ B| (1)
By meeting above-mentioned formula (1), there is not the face dazzle having the little internal diffusion of scattering angle caused by organic fine particles (A) and the large internal diffusion of the scattering angle caused by particulate (B) concurrently, the antiglare film of the excellent in uniformity of picture brightness can be obtained.
In addition, as the assay method of the refractive index of above-mentioned radiation curable bonding agent, organic fine particles (A) and particulate (B), any means can be enumerated, such as, Baker process can be passed through, the method for minimum deviation angle, angle of deviation are resolved, mode-line (モ ー De ラ イ Application) method, Ellipsometric etc. measure.In each method, except material itself is measured, also can material similarly for particulate having been taken out with some form in the film from made anti-glare film, or also can similarly for film itself according to the difference of assay method.
Further, when above-mentioned radiation curable bonding agent contains above-mentioned (methyl) acrylate and resin in addition and adjuvant, the refractive index that beyond the particulate after the refractive index of above-mentioned radiation curable bonding agent refers to removing solidification, contained all resins composition and adjuvant produce.
As the preferred assay method of above-mentioned refractive index, if radiation curable bonding agent, can enumerate and from cured film, only remove adhesive portion and carry out method for measuring by Baker process.In addition, measure phase differential by the infiltration type phase shift laser micro-interference determinator PLM-OPT using NTT Advanced Technology society to manufacture, can survey the refringence of organic fine particles and resinous principle.Thus, about the refractive index of organic fine particles, the method that the form can enumerating the refractive index ± refringence of the resinous principle previously obtained is obtained.
Above-mentioned coating fluid is preferably further containing solvent.
Be not particularly limited as above-mentioned solvent, can enumerate such as: alcohol (such as methyl alcohol, ethanol, isopropyl alcohol, butanols, phenmethylol), ketone (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone), ester (such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbon (such as hexane, cyclohexane), halogenated hydrocarbons (such as methylene chloride, chloroform, phenixin), aromatic hydrocarbon (such as benzene, toluene, dimethylbenzene), acid amides (such as dimethyl formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE), ether (such as diethyl ether, dioxane, tetrahydrofuran), ether alcohol (such as 1-methoxy-2-propanol) etc.
Above-mentioned radiation curable bonding agent and solvent all can be selected to have and the material of the swelling character of above-mentioned organic fine particles (A) is used, and also can only any one party select to have the material of the swelling character of above-mentioned organic fine particles (A) is used.
In addition, by there is the solvent with the character making this organic fine particles (A) swelling, can not rely on the degree of the swellability of above-mentioned radiation curable bonding agent and more reliably carry out the formation of the infiltration layer of above-mentioned organic fine particles (A), therefore more preferably at least above-mentioned solvent has the character making above-mentioned organic fine particles (A) swelling.Its reason is by inference, and first above-mentioned solvent acts on above-mentioned organic fine particles (A), and above-mentioned organic fine particles (A) occurs swelling, and the low molecular weight compositions infiltration contained by following above-mentioned radiation curing bonding agent is entered.
In anti-glare film of the present invention, as the combination of above-mentioned radiation curable bonding agent and solvent, wherein, as radiation curable bonding agent, the reason being easy to for molecular weight is little infiltrate uses (methyl) acrylate monomer, as solvent, make above-mentioned organic fine particles (A) that the strong ketone of swelling character and/or ester system occur, preferably they are combinationally used.
In addition, by by the degree of swelling adjusting organic fine particles (A) used in combination for above-mentioned solvent, the infiltration amount of the low molecular weight compositions contained by above-mentioned radiation curable bonding agent can be controlled.
In addition, when using cellulose triacetate (hereinafter also referred to as TAC base material) as Mght-transmitting base material, in order to diffusing layer and Mght-transmitting base material interface adaptation or produce interference fringe in order to prevent at interface, preferably using can swelling above-mentioned TAC base material and can make the solvent of low molecular weight compositions infiltration in TAC base material in solvent and resinous principle.Can also be identical for the swelling solvent of organic fine particles (A) with the solvent of infiltration in TAC base material.Namely, if to the solvent of TAC base material with previously prepared to have solvent used in the situation of the organic fine particles (A) of the layer that infiltrates roughly the same, compound balance then contained by above-mentioned coating fluid is in highly stable state, even if when the processing carrying out anti-glare film for a long time, also can stablize processing, can be made into excellent coating fluid.
As such solvent, preferable methyl isobutyl ketone etc.In addition, as the low molecular weight compositions in resinous principle, preferred pentaerythrite three (methyl) acrylate, pentaerythrite five (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
Above-mentioned coating fluid can by preparing above-mentioned each material mixing.
Be not particularly limited as the method that coating fluid is prepared in above-mentioned each material mixing, such as, use coating rocker or ball mill etc.
Above-mentioned diffusing layer can be formed as follows: by above-mentioned coating solution at least one face of above-mentioned Mght-transmitting base material, carry out drying to form film, make this curing of coating, thus form above-mentioned diffusing layer.
Coating process as above-mentioned coating fluid is not particularly limited, and can enumerate such as rolling method, mayer stick coating method, gravure, mould Tu Fa etc.
The thickness of film formed as the above-mentioned coating fluid of coating is not particularly limited, and the concaveconvex shape can considering to be formed on surface, the material etc. used suitably are determined.If more than 1 μm then painting property is excellent firmly, if less than 20 μm then not easily occur curling, be thus preferably 1 μm ~ about 20 μm.Be more preferably 2 μm ~ 15 μm, more preferably 2 μm ~ 10 μm.
The thickness of above-mentioned diffusing layer to be observed etc. by the section S EM of diffusing layer and is measured.When measuring, measuring the thickness of diffusing layer surface location to Mght-transmitting base material interface that never there is organic fine particles (A2) of more than 5, obtaining its mean value.
In addition, as mentioned above, utilize above-mentioned radiation curable bonding agent and/or solvent to make above-mentioned organic fine particles (A) swelling, carry out the infiltration of radiation curable bonding agent to form infiltration layer, thus suitably prepare organic fine particles (A2); The preparation of this organic fine particles (A2) can be carried out in above-mentioned coating fluid, carries out in the film that also can be formed being applied to above-mentioned Mght-transmitting base material.
By making to be formed in film generation solidification on above-mentioned Mght-transmitting base material to form diffusing layer.
Curing as above-mentioned film is not particularly limited, and carries out preferably by Ultraviolet radiation.When being cured by ultraviolet, preferably use the ultraviolet of 190nm ~ 380nm wave band.Metal halide lamp, high-pressure sodium lamp, low pressure mercury lamp, ultrahigh pressure mercury lamp, carbon arc lamp, biuret light fluorescent lamp etc. such as can be utilized to carry out based on ultraviolet solidification.As the concrete example of electronic radial source, can enumerate croft-Wa Erdun (コ ッ Network Network ロ Off ト ワ Le ト) type of examining, Vandegrift (バ Application デ グ ラ Off ト) type, resonance transformer type, insulating core transformer type, linear pattern, rummy (ダ イ Na ミ ト ロ Application) the various electron ray accelerator such as type, high-frequency type.
In addition, for making above-mentioned layered inorganic compound in diffusing layer in random orientation state, when the preparation of above-mentioned coating fluid, preference as use ultrasound wave etc. by electric neutrality such as talcums and the few layered inorganic compound of lattice imperfection and organic fine particles (A), radiation curable bonding agent and solvent etc. dispersed, make coating solution can not apply shearing stress (シ ェ ア ー) to during above-mentioned Mght-transmitting base material, make convection current reduce time dry and form film.By so forming film, the layered inorganic compound in this film can be made orientation not to occur, thereafter by making curing of coating, the diffusing layer laminate mineral compound formed contains with random orientation state.
In addition, further preferred in coating fluid, add 0.0002 quality % ~ 2.0 quality % fluorine system, the surfactant such as siloxane-based to be to obtain random state of orientation.This is because, by more effectively suppressing convection current during drying, and prevent the orientation caused by convection current.If addition is less than 0.0002 quality %, then the effect of convection current is suppressed to become insufficient; If more than 2.0 quality %, then reducing may appear in the hardness, mar resistance etc. of formed diffusing layer.
In anti-glare film of the present invention, above-mentioned diffusing layer has concaveconvex shape on surface.
At least with organic fine particles (A) the corresponding position of above-mentioned diffusing layer preferably in this diffusing layer has protuberance (hereafter also referred to as protuberance (A)).
In addition, when organic fine particles (A) for above-mentioned have infiltration layer organic fine particles (A2), the height of raised part (A) and/or average slope angle are preferably lower than height and/or the average slope angle of following protuberance (C), and this protuberance (C) is for meeting the protuberance (hereafter also referred to as protuberance (C)) of the position corresponding with above-mentioned organic fine particles (C) on the whole surface of the diffusing layer (C) containing organic fine particles (C) in following important document (1), (2) and (3).
Important document (1): except using organic fine particles (C) to come except alternative organic fine particles (A), utilize the condition same with the diffusing layer containing organic fine particles (A) to form diffusing layer (C)
Important document (2): the organic fine particles (C) in diffusing layer (C) has the identical mean grain size of organic fine particles (A) in diffusing layer
Important document (3): organic fine particles (C) does not form infiltration layer in diffusing layer (C)
For the protuberance (A) of the position corresponding with above-mentioned organic fine particles (A2), compared with raised part (C), height and/or average slope angle low, be mild shape.The anti-glare film of the present invention with the diffusing layer defining such protuberance (A) can have excellent anti-glare, preventing sheding tintability.
It is believed that, its reason is, compared with above-mentioned organic fine particles (C), above-mentioned organic fine particles (A2) is the particulate being imbued with very much flexibility.Namely, if make above-mentioned curing of coating, then radiation curable bonding agent causes cure shrinkage, compared with the cure shrinkage on the surface not residing with this organic fine particles (A2), the cure shrinkage on the surface residing for above-mentioned organic fine particles (A2) reduces because above-mentioned radiation curable amount of binder is few.In addition, because above-mentioned organic fine particles (A2) is the particulate being imbued with very much flexibility, thus organic fine particles (A2) can be out of shape due to the cure shrinkage of above-mentioned film.Its result, infer, for height and/or the average slope angle of formed protuberance (A), compared with the raised part (C) formed with the surface at the diffusing layer (C) containing harder organic fine particles (C), lower and smooth.
In addition, the height of raised part refers to, observes anti-glare film surface by AFM, is measured by the height n (n is 1 ~ 10) of the difference of the protuberance existing for surface and the recess between other protuberance adjacent with this protuberance as protuberance.Further, arbitrary 10 protrusion height of so trying to achieve are averaged, obtain the height of raised part.
In anti-glare film of the present invention, because layered inorganic compound above-mentioned in diffusing layer contains with random orientation state, even if thus when above-mentioned diffusing layer applies stress because distortion waits from various direction, also can prevent it from becoming the starting point of crackle.In addition, even if carry out Ultraviolet radiation when the making of this diffusing layer, the above-mentioned layered inorganic compound contained with random orientation state has also relaxed the infringement caused by Ultraviolet radiation, also can suitably prevent from producing in manufactured anti-glare film curling further.
That is, in anti-glare film of the present invention, contained with random orientation state in diffusing layer by above-mentioned layered inorganic compound, make it very excellent in resistance to impact.
Further, possess in the anti-glare film of the present invention of the diffusing layer containing above-mentioned organic fine particles (A2), because distortion waits the stress produced from various direction, distortion (askew body) caused by this stress is very serious, and the organic fine particles (A2) thus in this diffusing layer is very excellent with the adaptation of the solidfied material of radiation curable bonding agent.In addition, for anti-glare film of the present invention, in axle (マ Application De レ Le) test, at mandrel diameters be under the condition of 10mm, more preferably in the condition, preferred under the condition of 6mm further for 8mm, preferably do not crack.
In addition, organic fine particles (A2) in above-mentioned diffusing layer is formed with above-mentioned infiltration layer, this infiltration layer is that to be mixed with the shape of radiation curable bonding agent morphogenetic, therefore for above-mentioned diffusing layer, organic fine particles (A) (infiltration layer) in above-mentioned diffusing layer reduces with the refringence of the solidfied material of radiation curable bonding agent, suitably can reduce the reflection at interface.In addition, above-mentioned infiltration layer is the thickness of appropriateness simultaneously, and the center of organic fine particles (A) maintains the refractive index of the organic fine particles (A) at initial stage, thus can show the internal diffusion of appropriateness, can suitably prevent face dazzle.
Further, the height of the protuberance formed in the position corresponding with organic fine particles (A) of above-mentioned diffusing layer can be made low and be mild shape.
Therefore, it is possible to reach the anti-glare of anti-glare film of the present invention, preventing sheding tintability and anti-dazzle with high level.
The turbidity value of anti-glare film of the present invention is preferably less than 30%.If be greater than 30%, then anti-glare film of the present invention produces and fades, and the image quality of image display device is poor sometimes.
In addition, above-mentioned turbidity value is turbidity (mist degree) according to JIS-K7136 defined, uses nephelometer HR100 (in village society of color technical institute manufacture, trade name) to carry out measuring and the value that obtains.Further, the turbidity value in the present invention is the value utilizing the method to measure.
The method manufacturing such anti-glare film of the present invention is also one of the present invention.
Namely, the manufacture method of anti-glare film of the present invention is the manufacture method of the anti-glare film with Mght-transmitting base material and diffusing layer, this diffusing layer is formed at least one face of this Mght-transmitting base material, surface has concaveconvex shape, the method is characterized in that, it has following operation: will containing layered inorganic compound, organic fine particles (A) and comprise the coating solution of (methyl) acrylate monomer as the radiation curable bonding agent of neccessary composition at least one face of above-mentioned Mght-transmitting base material, carry out drying to form film, and make this curing of coating, form described diffusing layer, above-mentioned layered inorganic compound in above-mentioned diffusing layer contains with random orientation state.
In the manufacture method of anti-glare film of the present invention, the material etc. forming above-mentioned coating fluid can enumerate the material identical with material illustrated in the anti-glare film of the invention described above.
In addition, the operation forming above-mentioned diffusing layer also can enumerate the method identical with the method illustrated in the anti-glare film of the invention described above.
In addition, following polaroid is also one of the present invention, and this polaroid is the polaroid possessing polarization element, it is characterized in that, carries out the laminating etc. of Mght-transmitting base material, and possess anti-glare film of the present invention on the surface of above-mentioned polarization element.
Be not particularly limited as above-mentioned polarization element, such as, can use and utilize iodine etc. to carry out dyeing and the polyvinyl alcohol film stretched, polyvinyl formal film, polyvinyl acetal film, vinyl-vinyl acetate copolymer system saponification film etc.In the Stratificated treatment of above-mentioned polarization element and anti-glare film of the present invention, preferably saponification process is carried out to Mght-transmitting base material.By saponification process, cementability is good, and can obtain antistatic effect.
The invention still further relates to the image display device possessing above-mentioned anti-glare film or above-mentioned polaroid in outmost surface.Above-mentioned image display device can enumerate LCD, PDP, FED, ELD (organic EL, inorganic EL), CRT, touch-screen, Electronic Paper etc.
Above-mentioned LCD is by possessing permeability display body and forming from the light supply apparatus of the above-mentioned permeability display body of back side illuminaton.When image display device of the present invention is LCD, be form anti-glare film of the present invention or polaroid of the present invention on the surface of this permeability display body.
When the present invention is the liquid crystal indicator with above-mentioned anti-glare film, the light source of light supply apparatus irradiates from the downside of anti-glare film.In addition, in the liquid crystal indicator of STN type, can insertion phase difference plate between liquid crystal display cells and polaroid.Cement layers can be set as required at each interlayer of this liquid crystal indicator.
Above-mentioned PDP by possess watch crystal substrate and with this watch crystal substrate in opposite directions and the back glass substrate enclosed discharge gas therebetween and configured form.When image display device of the present invention is PDP, possesses above-mentioned anti-glare film on the surface of above-mentioned watch crystal substrate or its front panel (glass substrate or film substrate).
As other image display devices, can be to glass substrate evaporation irradiative zinc sulphide, Diamines material and luminophor when applying voltage, the ELD device that the voltage and carrying out controlling to be applied to substrate shows; Or for being light by transform electric, produce the image display devices such as the CRT of the image that human eye is seen.In this case, above-mentioned anti-glare film is possessed in the above-mentioned outmost surface of each display device or the surface of its front panel.
Anti-glare film of the present invention all can be used in the display screen display of televisor, computing machine etc. in all cases.Particularly, can suitably for the surface of liquid crystal panel, PDP, ELD, touch-screen, the contour precise image display screen of Electronic Paper.
Invention effect
In anti-glare film of the present invention, owing to containing with random orientation state at diffusing layer laminate mineral compound, even if thus when above-mentioned diffusing layer applies stress because distortion waits from various direction, also can prevent it from becoming the starting point of crackle.In addition, even if carry out Ultraviolet radiation when the making of this diffusing layer, the above-mentioned layered inorganic compound contained with random orientation state can relax the infringement caused by Ultraviolet radiation, also can suitably prevent manufactured anti-glare film from producing further curling.
Accompanying drawing explanation
Fig. 1 is the section S EM photo of the diffusing layer of the anti-glare film obtained in embodiment 1.
Embodiment
By following embodiment, content of the present invention is described, but and is not interpreted as content of the present invention is defined in these embodiments.
(embodiment 1)
First, as Mght-transmitting base material, prepare triacetyl cellulose (Fuji Photo Film Co., Ltd.'s manufacture, thickness 80 μm).
Next, as radiation curable bonding agent, use the potpourri (mass ratio of pentaerythritol triacrylate (PETA), dipentaerythritol acrylate (DPHA) and cellulose acetate-propionate (SAP), PETA/DPHA/SAP=82/7/11) (refractive index 1.51), as Photoepolymerizationinitiater initiater, use 1-hydroxy-cyclohexyl-phenyl-one: Irgacure184 (manufacture of BASF society) (be 3 mass parts relative to adhesive solids composition 100 mass parts), make wherein containing the low cross-linking acrylic particles (refractive index 1.49 as organic fine particles (A) relative to radiation curable bonding agent 100 mass parts being 6.0 mass parts, mean grain size 5.0 μm), relative to (the refractive index 1.59 of the granules of polystyrene as particulate (B) that radiation curable bonding agent 100 mass parts is 5.0 mass parts, mean grain size 3.5 μm), relative to (the refractive index 1.57 of the talc particle as layered inorganic compound that radiation curable bonding agent 100 mass parts is 8.0 mass parts, mean grain size 0.8 μm).Further interpolation is the non-reacted fluorine system surfactant as surfactant of 0.003 mass parts relative to radiation curable bonding agent 100 mass parts.Coordinating relative to radiation curable bonding agent 100 mass parts is wherein the toluene as solvent of 190 mass parts and the potpourri (mass ratio 8:2) of methyl isobutyl ketone, prepares coating fluid.
The mode of obtained coating fluid according to coating fluid quantity delivered consistent with coating weight (coating fluid quantity delivered/coating weight=1.0) is adjusted, thus be applied on Mght-transmitting base material without shearing stress by heliogravure, the dry air of 70 DEG C is circulated with the flow velocity of 1.2m/s, within dry 1 minute, forms film.
Thereafter, to film irradiation ultraviolet radiation (under nitrogen atmosphere, 200mJ/cm 2), radiation curable bonding agent is solidified, forms diffusing layer, make anti-glare film.In addition, the thickness of diffusing layer is 6.0 μm.
(embodiment 2 ~ 11, comparative example 1 ~ 5)
Make the organic fine particles (A) that adds in coating fluid and the kind of particulate (B), the kind of layered inorganic compound and content, the presence or absence of surfactant and (coating fluid quantity delivered/coating weight) ratio as shown in table 1, in addition, anti-glare film is made similarly to Example 1.
Table 1
The details of the organic fine particles (A) shown in table 1, particulate (B), layered inorganic compound and the mark shown in solvent is as described below.In addition, in Table 1, the content of layered inorganic compound represents the content (mass parts) relative to radiation curable bonding agent 100 mass parts.
(organic fine particles A)
A: high crosslinked acrylic particles (refractive index 1.49, mean grain size 5.0 μm, combine grind chemical society manufacture)
B: low cross-linking acrylic particles (refractive index 1.49, mean grain size 5.0 μm, combine grind chemical society manufacture)
(particles B)
C: granules of polystyrene (refractive index 1.59, mean grain size 3.5 μm, combine grind chemical society manufacture)
(layered inorganic compound)
M: talcum (refractive index 1.57, mean grain size 0.8 μm, nano-talc, Japanese talcum society manufacture)
N: bentonitic clay (refractive index 1.52, mean grain size 0.1 ~ 0.5 μm, Kunipia F, Kunimine industry society manufacture)
In addition, the particle diameter of layered inorganic compound is the mean grain size D50 utilizing laser diffraction and scattering formula particle size distribution method to record.
(solvent)
Y: the potpourri (mass ratio 8:2) of toluene and methyl isobutyl ketone
Z: the potpourri (mass ratio 7:3) of toluene and isopropyl alcohol
Following evaluation is carried out for the anti-glare film obtained in embodiment and comparative example.It the results are shown in table 2.
(the random orientation state of layered inorganic compound)
The anti-glare film obtained in embodiment and comparative example is cut off at thickness direction, in the cross section of diffusing layer, SEM observation is carried out in the region that thickness to this diffusing layer is formed with the vertical direction (10 μm) relative to this thickness direction, evaluates the state of orientation of layered inorganic compound.In addition, the section S EM photo of the diffusing layer of the anti-glare film of embodiment 1 has been shown in Fig. 1.
◎: among observed layered inorganic compound, the extended line of the extended line of its major diameter or major diameter and the major diameter of other layered inorganic compound or major diameter parallel to be less than 20% existence
Zero: among observed layered inorganic compound, what the extended line of the extended line of its major diameter or major diameter and the major diameter of other layered inorganic compound or major diameter was parallel is less than 30% existence with more than 20%
×: among observed layered inorganic compound, parallel the existing with more than 30% of extended line of the extended line of its major diameter or major diameter and the major diameter of other layered inorganic compound or major diameter
(turbidity)
According to the turbidity (mist degree) of JIS-K7136 defined, use nephelometer HR100 (in village, society of color technical institute manufactures), the turbidity value of the anti-glare film obtained in embodiment and comparative example is measured.
(axle test)
According to JIS K5600, carry out the axle test of the anti-glare film obtained in embodiment and comparative example with the axle of φ 6mm, φ 8mm and φ 10mm, evaluate according to following benchmark.
◎: do not crack with φ 6mm
Zero: do not crack with φ 8mm
△: do not crack with φ 10mm
×: crack with φ 10mm
(contrast)
Use blooming transparent adhesion film the anti-glare film obtained in embodiment and comparative example and black acrylic (acrylic acid) plate to be fitted, under the bright room condition of 1000Lx, carry out visual sense evaluation from various direction to the surface state of anti-glare film by 20 measured.Judge whether to reproduce the glossiness black of tool, and evaluate according to following benchmark.
◎: answering good people is more than 15 people
Zero: answering good people is 10 ~ 14 people
△: answering good people is 5 ~ 9 people
×: answering good people is below 4 people
(face dazzle)
The polaroid of the outmost surface of the liquid crystal TV set " KDL-40X2500 " society of Sony manufactured is peeled off, and attaches the polaroid without surface coating.
Next, the mode that blooming transparent adhesion film (total light transmittance more than 91%, turbidity less than 0.3%, the goods of thickness 20 ~ 50 μm, such as MHM series: Rong Chemical Co., Ltd manufactures) is outmost surface according to diffusing layer side is utilized to attach the anti-glare film obtained in embodiment and comparative example thereon.
This liquid crystal TV set being arranged on illumination is indoor under about 1,000Lx environment, carries out white screen display and shows, by measured 20 people from the position of distance liquid crystal TV set about 1.5 ~ 2.0m, carry out visual sense evaluation from upper and lower, the various angle in left and right.Judge whether confirm face dazzle in white screen display is shown, evaluate according to following benchmark.
◎: answering good people is more than 15 people
Zero: answering good people is 10 ~ 14 people
△: answering good people is 5 ~ 9 people
×: answering good people is below 4 people
(thickness of the infiltration layer of organic fine particles (A))
Anti-glare film is cut off at thickness direction, is observed by the SEM in diffusing layer cross section, 2 mensuration are respectively carried out to the thickness of the infiltration layer that the section of 5 organic fine particles (A) is formed, add up to and carry out 10 mensuration, calculate its mean value.
Table 2
As shown in table 2, for the anti-glare film of embodiment, carry out SEM cross-section, result layered inorganic compound contains with random orientation state in diffusing layer, in cross section, talc particle is observed with the form of the wire material of major diameter about 0.5 μm ~ about 1.5 μm, and bentonite clay particle is observed with the form of the wire material of about about 0.1 ~ 0.8 μm, and each evaluation of the test of turbidity value, axle, contrast and face dazzle is good.
In the anti-glare film of comparative example 1, due in diffusing layer not containing layered inorganic compound, each evaluation of thus axle test, contrast and face dazzle is poor.In the anti-glare film of comparative example 2, the content of the layered inorganic compound added when prepared by coating fluid is few, and each evaluations of axle test, contrast and face dazzle is poor, and layered inorganic compound is to be not the also more of random state of orientation existence.In addition, in the anti-glare film of comparative example 3, the content of the layered inorganic compound added when prepared by coating fluid is many, cannot be coated with uniformly on transparent base material.In addition, in the anti-glare film of comparative example 4 and 5, the layered inorganic compound in diffusing layer is not much in random orientation state, and each evaluation of axle test, contrast and face dazzle is poor.
Industrial applicibility
Anti-glare film of the present invention can suitably in display screen, the particularly high-precision refinement display screens such as CRT display (CRT), LCDs (LCD), plasma display panel (PDP) (PDP), electroluminescent display panel (ELD), touch-screen, Electronic Paper.

Claims (9)

1. an anti-glare film, it is the anti-glare film with Mght-transmitting base material and diffusing layer, and this diffusing layer is formed at least one face of this Mght-transmitting base material, and the surface of this diffusing layer has concaveconvex shape, it is characterized in that,
Described diffusing layer is by coating solution containing layered inorganic compound, organic fine particles (A) and radiation curable bonding agent and surfactant is carried out drying to form film at least one face of described Mght-transmitting base material, make this curing of coating, described radiation curable bonding agent comprises (methyl) acrylate monomer as neccessary composition;
There is not the orientation caused by the convection current of described coating fluid and contain with random orientation state in layered mineral compound, the mean grain size of layered mineral compound is 0.3 μm ~ 5 μm in described diffusing layer.
2. anti-glare film as claimed in claim 1, it is characterized in that, layered inorganic compound is talcum.
3. anti-glare film as claimed in claim 1 or 2, it is characterized in that, coating fluid contains the solvent of swelling organic fine particles (A).
4. the anti-glare film as described in claim 1,2 or 3, it is characterized in that, coating fluid is further containing particulate (B), and the organic fine particles (A) in diffusing layer has the infiltration layer that is impregnated with radiation curable bonding agent and has the mean grain size larger than the mean grain size of the particulate (B) in described diffusing layer.
5. anti-glare film as claimed in claim 4, it is characterized in that, particulate (B) is for lipophilicity is higher than the particulate of organic fine particles (A).
6. the anti-glare film as described in claim 4 or 5, it is characterized in that, the specific refractivity of the refractive index of radiation curable bonding agent and the specific refractivity of organic fine particles (A) and the refractive index of radiation curable bonding agent and particulate (B) is being set to Δ respectively aand Δ btime, described Δ aand Δ bmeet following following formula (1):
|Δ A|<|Δ B| (1)。
7. a manufacture method for anti-glare film, it is the manufacture method of the anti-glare film with Mght-transmitting base material and diffusing layer, and this diffusing layer is formed at least one face of this Mght-transmitting base material, and the surface of this diffusing layer has concaveconvex shape, it is characterized in that,
Described manufacture method has following operation: coating solution containing layered inorganic compound, organic fine particles (A) and radiation curable bonding agent and surfactant is carried out drying to form film at least one face of described Mght-transmitting base material, make this curing of coating and form described diffusing layer, wherein said radiation curable bonding agent comprises (methyl) acrylate monomer as neccessary composition;
There is not the orientation caused by the convection current of described coating fluid and contain with random orientation state in the layered mineral compound in described diffusing layer, the mean grain size of layered mineral compound is 0.3 μm ~ 5 μm.
8. a polaroid, is characterized in that, it is the polaroid possessing polarization element,
The anti-glare film described in claim 1,2,3,4,5 or 6 is possessed on the surface of described polarization element.
9. an image display device, is characterized in that, possesses anti-glare film described in claim 1,2,3,4,5 or 6 or polaroid according to claim 8 in the outmost surface of described image display device.
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