CN103119480A - Method for manufacturing optical film - Google Patents

Method for manufacturing optical film Download PDF

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Publication number
CN103119480A
CN103119480A CN2011800451299A CN201180045129A CN103119480A CN 103119480 A CN103119480 A CN 103119480A CN 2011800451299 A CN2011800451299 A CN 2011800451299A CN 201180045129 A CN201180045129 A CN 201180045129A CN 103119480 A CN103119480 A CN 103119480A
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functional layer
mentioned
coating
blooming
matrix
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CN103119480B (en
Inventor
西村明宪
泷田智仁
中村恒三
武本博之
渊田岳仁
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Nitto Denko Corp
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    • G02B1/105—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • 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
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles

Abstract

Provided is a method for manufacturing an optical film excellent in optical homogeneity and abrasion resistance and having at least a two-layer structure. This manufacturing method includes: a first coating step of coating one surface of a base film with a first coating containing a fluorine-based leveling agent having no reactive group to form a first functional layer; and a second coating step of coating the surface of the first functional layer with a second coating to form a second functional layer. The fluorine-based leveling agent is mostly distributed in the surface of the first functional layer when the second coating is applied, and is eluted into the second coating after the application of the second coating, and is then mostly distributed in the surface of the formed second functional layer.

Description

The manufacture method of blooming
Technical field
The present invention relates to a kind of manufacture method of blooming.
Background technology
In order to improve the display quality of liquid crystal indicator, improve viewing angle characteristic, utilize at present the bloomings such as light diffusion element.Light diffusion element for example possess performance light diffusion optical diffusion film, and reduce or mirror the anti-reflection layer of image for preventing by the contrast ratio that the reflection exterior light causes, and be disposed at the front surface of liquid crystal indicator.
In liquid crystal indicator, if the thickness heterogeneity of blooming can make the internal homogeneity (optics homogeneity) of optical characteristics reduce.As the technology that makes the thickness homogenization, during forming, known coating at blooming use levelling agent to make the thickness homogeneous (for example patent documentation 1) of blooming.But, during for the situation of the blooming of multi-ply construction, make the adhesion variation of interlayer because there is levelling agent in the bed interface, and can't obtain sufficient mar resistance as above-mentioned diffused component.Like this inadequate situation of mar resistance especially for the blooming of the header board that is disposed at liquid crystal indicator as described above, becomes problem aspect practical application.
[conventional art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2002-361769 communique
Summary of the invention
The present invention be for solve above-mentioned in the past problem and and the invention of completing, its purpose is, the manufacture method of the blooming that is at least 2 layers of structure of a kind of optics homogeneity and excellent scratch resistance is provided.
[technological means of dealing with problems]
Manufacture method of the present invention, comprise: on the one side of base material film coating contain the fluorine with reactive group be the 1st coating liquid of levelling agent and form the 1st functional layer the 1st working procedure of coating, and form the 2nd working procedure of coating of the 2nd functional layer at the surface of the 1st functional layer coating the 2nd coating liquid, and this fluorine is that levelling agent is that partially the 1st functional layer is surperficial when coating the 2nd coating liquid, be eluted to the 2nd coating liquid after coating the 2nd coating liquid in, be that partially the 2nd functional layer that forms is surperficial.
In preferred embodiment, above-mentioned fluorine is that levelling agent contains freely at least a kind of structural unit in the group that forms of the represented structural unit of represented structural unit, the following general formula (II) of following general formula (I) and the represented structural unit of following general formula (III) of choosing
[changing 1]
Figure BDA00002939928600021
-O-CF 2-O- …(III)
In general formula (I), m is 1～10 integer, and in general formula (II), n is 2～10 integer.
In preferred embodiment, above-mentioned fluorine is that the content of levelling agent is 0.05 % by weight～3 % by weight with respect to the whole solid state components in above-mentioned the 1st coating liquid.
In preferred embodiment, above-mentioned the 1st functional layer is light diffusion layer.
In preferred embodiment, above-mentioned the 2nd functional layer is anti-reflection layer.
In preferred embodiment, above-mentioned light diffusion layer has matrix and the light diffusing particulate that is dispersed in this matrix, form the index modulation zone that refractive index changes in fact continuously at the interface of this matrix and this light diffusing particulate or near it, and satisfy following formula (3) and (4)
Δn≥0.10 …(3)
0.0006≤Δn/L≤0.01 …(4)
Here, Δ n is the mean refractive index n of matrix MRefractive index n with the light diffusing particulate PThe absolute value of difference | n M-n P|, L is the average thickness in index modulation zone.
In preferred embodiment, n M＞n P
In preferred embodiment, above-mentioned light diffusion layer satisfies formula (5),
0.01≤L/r P≤1.0 …(5)
Here, r PRadius for above-mentioned light diffusing particulate.
In preferred embodiment, above-mentioned matrix contains resinous principle and ultra micron composition, and the substantive gradient that above-mentioned index modulation zone is based on the dispersion concentration of this ultra micron composition in this matrix forms.
In preferred embodiment, above-mentioned light diffusion layer satisfies formula (1),
|n P-n A|＜|n P-n B| …(1)
Here, n AThe refractive index of the resinous principle of expression matrix, n BThe refractive index of the ultra micron composition of expression matrix.
[effect of invention]
Manufacture method of the present invention comprise coating contain fluorine be the 1st coating fluid of levelling agent and form the 1st functional layer the 1st working procedure of coating, and form the 2nd working procedure of coating of the 2nd functional layer at the 1st functional layer surface coating the 2nd coating fluid.The fluorine that uses in manufacture method of the present invention to be levelling agent be when coating the 2nd coating liquid partially the 1st functional layer surface is eluted to the 2nd coating liquid after coating the 2nd coating liquid, the 2nd functional layer surface that partially is to form.The blooming that obtains by above-mentioned manufacture method is excellent aspect optics homogeneity and mar resistance.
Description of drawings
Figure 1A is the schematic diagram for the formation that the blooming that obtains by manufacture method preferred embodiment of the present invention is described.
Figure 1B is that the light that amplifies the 1st functional layer of Figure 1A spreads near the schematic diagram that is illustrated particulate.
Fig. 2 is the concept map of the 1st functional layer from light diffusing particulate central part to the variations in refractive index of matrix for explanation Figure 1A.
Fig. 3 is the through mode electron microscope image for the area ratio of the ultra micron composition of explanation matrix.
Fig. 4 (a) is for the mean refractive index n of explanation in matrix MThe refractive index n of＞light diffusing particulate PSituation the time produce the concept map of backward scattered mechanism, be (b) at n for explanation M＜n PSituation the time produce the concept map of backward scattered mechanism.
Fig. 5 calculates the schematic diagram of the method for light diffusion half-value angle for explanation.
Fig. 6 means that the fluorine in embodiment 1 and comparative example 1 is the figure of the distribution of levelling agent on the blooming section.
Fig. 7 means the figure of the fluorine atom concentration on the blooming section of embodiment 1.
Embodiment
A. the 1st working procedure of coating
The 1st working procedure of coating of manufacture method of the present invention, to comprise fluorine be the 1st coating liquid of levelling agent and form the 1st functional layer in coating on the one side of base material film.The 1st working procedure of coating is included on the one side of base material film coating the 1st coating liquid and makes the coated film of the 1st coating liquid that is formed on base material film dry.The 1st functional layer for example can be the light diffusion layer of performance light diffusion function.
Above-mentioned the 1st coating liquid preferably comprises resinous principle or its precursor.In addition, when above-mentioned the 1st functional layer was the situation of light diffusion layer, the 1st coating liquid preferably comprised matrix and forms material and light diffusing particulate, and this matrix forms material and comprises resinous principle or its precursor and ultra micron composition.
Representative is above-mentioned the 1st coating liquid is dispersed with fluorine in the precursor of resinous principle and volatile solvent be the dispersion that levelling agent, ultra micron composition and light diffusing particulate form.As the means that make ultra micron composition and light diffusing microparticulate, can adopt arbitrarily suitable means (for example ultrasound wave is processed, the dispersion treatment by stirring machine).
Above-mentioned fluorine is that levelling agent does not have reactive group.If using the fluorine do not have reactive group is levelling agent, be combined because of the resinous principle in the 1st coating liquid not, so in aftermentioned the 2nd working procedure of coating, easily be eluted in the 2nd coating liquid.
Above-mentioned fluorine is that levelling agent is in the 1st working procedure of coating, at above-mentioned the 1st coating liquid of coating and the coated film that forms surface deflection exists.If using such fluorine is levelling agent, when the 1st working procedure of coating dry, the thin layer that becomes fluorine and be levelling agent covers the state on coated film surface.The surface tension of the coated film of such state is lower and the evaporation rate of solvent coating liquid when dry is slower.Therefore, surface tension in the coated film that heating in the time of can reducing mainly due to drying uneven (for example the heat in baking oven is uneven, the contact of the wind (following stream) that produces due to transport membrane uneven) produces is poor, the generation of the thermal convection that the inhibition coated film is interior.Its result, the 1st functional layer that obtains through such drying, thickness and precision is excellent, and the optics homogeneity is excellent.
Be levelling agent as the fluorine that can so be partial to existence, for example can enumerate: the fluorine that comprises at least a kind of structural unit in the group that the represented structural unit of the structural unit that selects following general formula (I) represented, following general formula (II) and the represented structural unit of following general formula (III) form is levelling agent.
[changing 2]
Figure BDA00002939928600051
-O-CF 2-O- …(III)
In general formula (I), m is preferably 1～10 integer, and then is preferably 2～8 integer.In general formula (II), n is preferably 2～10 integer, and then is preferably 4～8 integer.
Reaching (III) by above-mentioned general formula (I), (II), the total of represented structural unit contains proportional, be the total amount of the structural unit of levelling agent with respect to consisting of above-mentioned fluorine, be preferably 10mol%～100mol%, and then be preferably 20mol%～70mol%.
Preferred above-mentioned fluorine is that levelling agent contains at least one by the represented structural unit of above-mentioned general formula (III).Comprise if use the 1st coating liquid that the fluorine with such structural unit is levelling agent, in the coated film that forms at this coating liquid of coating, fluorine is that the movement of levelling agent accelerates, and can make fluorine is that levelling agent is partially that efficiently this coated film is surperficial.
Above-mentioned fluorine is that the number of the ehter bond that has of levelling agent is preferably more than 2, and then is preferably 4～30, is particularly preferably 6～20.Above-mentioned fluorine be levelling agent owing to containing more ehter bond, flexibility is higher.
The molecular weight of above-mentioned fluorine levelling agent is preferably 50～2000, and then is preferably 100～1500.If such scope, can make more fluorine is the surface that levelling agent is above-mentioned the 1st functional layer partially.
Fluorine is the use level of levelling agent, with respect to the whole solid state components in the 1st coating liquid, be preferably 0.05 % by weight～3 % by weight, more preferably 0.1 % by weight～2.5 % by weight, and then be preferably 0.2 % by weight～1.0 % by weight, be particularly preferably 0.3 % by weight～0.8 % by weight.
Above-mentioned resinous principle can be made of any suitable resin.Preferably consisted of by organic compound, more preferably consisted of by ionization ray solidified resin.Ionization ray solidified resin is excellent because of the hardness of filming, therefore can form the 1st functional layer of physical strength excellence.As ionization property ray, for example can enumerate ultraviolet ray, visible light, infrared ray, electron ray.Preferred ultraviolet ray, therefore, resinous principle particularly preferably is made of ultraviolet curing resin.As ultraviolet curing resin, such as enumerating acrylate resin (epoxy acrylate, polyester acrylate, acrylic acrylate (acrylic acrylate), ether acrylate) etc. by radical polymerization mould assembly monomer or oligomer and the resin that forms.The molecular weight that consists of the monomer component (precursor) of acrylate resin is preferably 200～700.Molecular weight 298), neopentylglycol diacrylate (NPGDA: molecular weight 212), dipentaerythritol acrylate (DPHA: molecular weight 632), dipentaerythritol five acrylate (DPPA: molecular weight 578), trimethylolpropane triacrylate (TMPTA: molecular weight 296) as the concrete example of the monomer component (precursor) that consists of acrylate resin, can enumerate pentaerythritol triacrylate (PETA:.Also can add initiating agent in precursor as required.As initiating agent, such as enumerating UV free-radical generating agent (BASF Japan company makes Irgacure907, Irgacure127, Irgacure192 etc.), benzoyl peroxide base.Above-mentioned resinous principle also can comprise other resinous principles except above-mentioned ionization ray solidified resin.Other resinous principles can be ionization ray solidified resin, also can be heat-curing resin, also can be thermoplastic resin.As the typical example of other resinous principles, can enumerate fatty family (for example polyolefin) resin, polyurethane series resin.
When above-mentioned the 1st functional layer was the situation of light diffusion layer, the 1st functional layer preferably had matrix and is dispersed in light diffusing particulate in this matrix.Above-mentioned light diffusion layer is that the refringence by matrix and light diffusing particulate shows light diffusion function.Preferably the near interface formation index modulation at matrix and light diffusing particulate is regional in above-mentioned light diffusion layer.In the index modulation zone, refractive index changes in fact continuously.In this instructions, as long as " refractive index changes in fact continuously " refers in the index modulation zone the constant zone from the light diffusing microparticle surfaces to refractive index at least, and refractive index changes in fact continuously and gets final product.Obtainable according to the present invention have light diffusion layer and describe in B item described later as the detailed content of the blooming of the 1st functional layer.
Form the material (matrix formation material) of above-mentioned matrix, comprise above-mentioned resinous principle or its precursor, reach the ultra micron composition.
Above-mentioned matrix forms in material, and the use level of above-mentioned resinous principle is preferably 10 weight portions～80 weight portions with respect to matrix 100 weight portions, more preferably 20 weight portions～65 weight portions.
The constituent material of the resinous principle of above-mentioned matrix and ultra micron composition and light diffusing particulate and chemistry and thermodynamics characteristic can be selected in the scope that can form above-mentioned index modulation zone.For example, by making resinous principle and light diffusing particulate comprise the material (for example organic compound each other) of homology, the ultra micron composition is comprised and resinous principle and the light diffusing particulate material of homology (for example mineral compound) not, can form preferably the index modulation zone.And then preference is as comprising with the higher material of intermiscibility in based material each other resinous principle and light diffusing particulate.The thickness in index modulation zone and refractive index gradient can be controlled by the resinous principle of adjustment matrix and chemistry and the thermodynamics characteristic of ultra micron composition and light diffusing particulate.Need to prove, in this manual " homology " refer to chemical constitution or characteristic identical or similar, homology except " not homology " refers to.Whether be homology, can be according to the system of selection of benchmark and difference.For example during the situation take organic or inorganic as benchmark, organic compound is the compound of homology each other, and organic compound and mineral compound are the compound of homology not.During situation take the repetitive of polymkeric substance as benchmark, although for example acrylic acid series polymeric compounds and epoxy based polymer are all organic compound, belong to the not compound of homology; During situation take periodic table as benchmark, although alkaline metal and transition metal are all inorganic elements, belong to the not element of homology.
Above-mentioned ultra micron composition preferably contains and above-mentioned resinous principle and the light diffusing particulate described later compound of homology not as mentioned above, more preferably contains mineral compound.As preferred mineral compound, for example can enumerate metal oxide, metal fluoride.2.19), aluminium oxide (refractive index: 1.56～2.62), titanium dioxide (refractive index: 2.49～2.74), monox (refractive index: 1.25～1.46) as the concrete example of metal oxide, can enumerate zirconia (zirconia) (refractive index:.1.37), calcium fluoride (refractive index: 1.40～1.43) as the concrete example of metal fluoride, can enumerate magnesium fluoride (refractive index:.These metal oxides and metal fluoride are less because absorbing light, and has the refractive index that the organic compounds such as ionization ray solidified resin or thermoplastic resin are difficult for performance, therefore follow away from relative uprising, refraction index modulation greatly with the interface of light diffusing particulate by the weight concentration of ultra micron composition.Become large by the refringence that makes light diffusing particulate and matrix, even film also can be realized high diffusion, and because of formation index modulation zone, therefore prevent that backward scattered effect is also larger.Particularly preferred mineral compound is zirconia.
The average primary particle diameter of above-mentioned ultra micron composition is preferably less than the average thickness L in index modulation zone.More specifically, average primary particle diameter is preferably 1/50～1/2 with respect to average thickness L, and more preferably 1/25～1/3.If average primary particle diameter surpasses 1/2 with respect to average thickness L, the not continuous in fact situation of variations in refractive index in index modulation zone is arranged.Lower than 1/50 situation the time, the become situation of difficulty of the formation in index modulation zone is arranged.Above-mentioned average primary particle diameter is preferably 1nm～100nm, more preferably 1nm～50nm.But the also secondary aggegation of ultra micron composition, the mean grain size during this situation (mean grain size of agglutination body) is preferably 10nm～100nm, more preferably 10nm～80nm.So, by using mean grain size less than the ultra micron composition of light wavelength, can make geometrical optics sexual reflex, refraction, scattering do not occur between ultra micron composition and resinous principle, can obtain the matrix of optical homogeneous.Its result can obtain the light diffusion layer of optical homogeneous.
Preferred above-mentioned ultra micron composition is carried out surface modification.By carrying out surface modification, the ultra micron composition is disperseed in resinous principle preferably and can form preferably above-mentioned index modulation zone.As the means of surface modification, as long as can obtain effect of the present invention, can adopt suitable means arbitrarily.Representative is that surface modification forms the surface modifier layer by the surface-coated surface modifier at the ultra micron composition and carries out.As the concrete example of preferred surface modifier, can enumerate silane is that coupling agent, titanate esters are the surfactants such as coupling agent, fatty acid series surfactant such as coupling agent.By using such surface modifier, the wetting state of resinous principle and ultra micron composition is improved, make the interface of resinous principle and ultra micron composition become stable, the ultra micron composition is disperseed in resinous principle preferably and can form preferably the index modulation zone.
The use level of above-mentioned ultra micron composition is preferably 15 weight portions～80 weight portions with respect to matrix 100 weight portions, and then is preferably 20 weight portions～70 weight portions.
Above-mentioned light diffusing particulate can be made of any suitable material.Preferably be made of the material that can form preferably above-mentioned index modulation zone, as mentioned above, the light diffusing particulate is to be made of the compound with the resinous principle homology of above-mentioned matrix.For example, when the ionization ray solidified resin of the resinous principle that consists of matrix was the situation of acrylic ester resin, preferred light diffusivity particulate also was made of the acrylic ester resin.More specifically, when the monomer component of the acrylic ester resin of the resinous principle that consists of matrix is the situation of example PETA described above, NPGDA, DPHA, DPPA and/or TMPTA, consist of the acrylic ester resin of light diffusing particulate, be preferably polymethylmethacrylate (PMMA), polymethyl acrylate (PMA, poly (methyl acrylate)), their multipolymer, and these cross-linking agent.As the copolymer composition of PMMA and PMA, can enumerate polyurethane, polystyrene (PSt), melamine resin.Particularly preferably the light diffusing particulate is made of PMMA.Its reason is, and is more suitable in the relation aspect refractive index and thermodynamics characteristic with resinous principle and the ultra micron composition of matrix.And then preferred light diffusivity particulate has crosslinked configuration (space network).By adjusting the density (degree of crosslinking) of crosslinked configuration, can be controlled in the degree of freedom that the light diffusing microparticle surfaces consists of the polymer molecule of particulate, therefore can control the disperse state of ultra micron composition, as a result of, can form the index modulation zone with required refractive index gradient.For example, the coating coating liquid the time the light diffusing particulate be preferably 100%～200% with respect to the swellbility of resinous principle precursor (also can comprise solvent).Here, so-called " swellbility " is the index of degree of crosslinking, the ratio of the mean grain size of the particle of the mean grain size of particle that refers to solvent swelling state before with respect to swelling.
The mean grain size of above-mentioned light diffusing particulate is preferably 1.0 μ m～5.0 μ m, more preferably 1.0 μ m～4.0 μ m.The mean grain size of light diffusing particulate is preferably below 1/2 of thickness (for example 1/2～1/20) of light diffusion layer.If have the mean grain size of such ratio with respect to the thickness of light diffusion layer, can make the light diffusing particulate arrange a plurality of at the thickness direction of light diffusion layer, therefore this light is spread, and its result can obtain sufficient light diffusing multiplely.
The standard deviation that the weight average particle diameter of above-mentioned light diffusing particulate distributes is preferably below 1.0 μ m, more preferably below 0.5 μ m.If be mixed with a large amount of particle diameters light diffusing particulate less with respect to weight average particle diameter, there be diffusivity excessively to increase and can't suppress preferably backward scattered situation.If be mixed with a large amount of particle diameters light diffusing particulate larger with respect to weight average particle diameter, can't arrange at the thickness direction of light diffusion layer a plurality ofly, sometimes can't obtain MULTIPLE DIFFUSION, its result has the light diffusing inadequate situation that becomes.
As the shape of above-mentioned light diffusing particulate, can adopt suitable shape arbitrarily according to purpose.As concrete example, can enumerate just spherical, flakey, tabular, oval spherical or irregularly shaped.During most situation, can use positive spheroidal particle as above-mentioned light diffusing particulate.
The use level of above-mentioned light diffusing particulate is preferably 10 weight portions～100 weight portions with respect to matrix 100 weight portions, 10 weight portions～40 weight portions more preferably, and then be preferably 10 weight portions～35 weight portions.By for example contain the light diffusing particulate of the mean grain size with above-mentioned preferable range with such use level, can form the light diffusion layer with very excellent light diffusing.
What above-mentioned resinous principle, ultra micron composition and light diffusing particulate were representative is to satisfy following formula (1):
|n P-n A|＜|n P-n B| …(1)
In formula (1), n AThe refractive index of the resinous principle of expression matrix, n BThe refractive index of the ultra micron composition of expression matrix, n PThe refractive index of expression light diffusing particulate.And then resinous principle also can satisfy following formula (2):
|n P-n A|＜|n A-n B| …(2)
The refractive index of resinous principle is preferably 1.40～1.60.The refractive index of ultra micron composition is preferably below 1.40 or more than 1.60, and then is preferably below 1.40 or 1.70～2.80, is particularly preferably below 1.40 or 2.00～2.80.If refractive index is over 1.40 or lower than 1.60, the refringence of light diffusing particulate and matrix becomes insufficient, before the blooming with light diffusion layer be used for to adopt collimated back during the situation of the liquid crystal indicator of diffusion (front diffusion) system, have light from collimated back fully to spread and make the visual angle narrow may.The refractive index of light diffusing particulate is preferably 1.30～1.70, and then is preferably 1.40～1.60.
As above-mentioned volatile solvent, as long as can make above-mentioned each composition dissolving or disperse equably, can adopt suitable solvent arbitrarily.As the concrete example of volatile solvent, can enumerate ethyl acetate, butyl acetate, isopropyl acetate, 2-butanone (methyl ethyl ketone), methyl isobutyl ketone, cyclopentanone, toluene, isopropyl alcohol, normal butyl alcohol, cyclopentane, water.
Above-mentioned the 1st coating liquid can and then contain suitable adjuvant arbitrarily according to purpose.For example, disperse preferably in order to make the ultra micron composition, can preferably use spreading agent.As other concrete examples of adjuvant, can enumerate ultraviolet light absorber, defoamer.
The solid component concentration of above-mentioned the 1st coating liquid preferably can tune to about 10 % by weight～70 % by weight.If such solid component concentration can obtain to have the coating liquid that coating is easy to viscosity.
In above-mentioned the 1st coating liquid, use methyl ethyl ketone as volatile solvent, the surface tension the when fluorine that contains general assembly (TW) with respect to the 1st coating liquid and be 27.5 % by weight is levelling agent is preferably 10mN/m～32mN/m, and then is preferably 20mN/m～30mN/m.If such scope, in the time of can reducing mainly due to drying heating uneven and surface tension in the coated film that produces is poor, can be suppressed at the thermal convection that produces in coated film.Its result, the light diffusion layer that obtains through such drying, thickness and precision is excellent, and in face, the homogeneity of brightness is high.
As above-mentioned base material film, can adopt suitable film arbitrarily.As concrete example, can enumerate triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, polypropylene (PP) film, nylon membrane, acrylic film, lactone modified propylene sorrel etc.Above-mentioned base material film also can through surface modifications such as easy bonding processing, also can comprise the adjuvants such as lubricant, antistatic agent, ultraviolet light absorber as required.
The thickness of above-mentioned base material film is preferably 20 μ m～80 μ m, and then is preferably 30 μ m～60 μ m.
Above-mentioned base material film is preferably transparent.Particularly, the total light transmittance of above-mentioned base material film is preferably more than 80%, and then is preferably more than 90%, is particularly preferably more than 95%.
As the coating process of above-mentioned the 1st coating liquid to base material film, the method for coating machine that can adopt arbitrarily suitable use.As the concrete example of coating machine, can enumerate that rod is coated with machine, oppositely coating machine, kiss coater, intaglio printing coating machine, mould are coated with machine, spot printing machine (comma coater).
As the drying means of above-mentioned the 1st coating liquid, can adopt suitable method arbitrarily.As concrete example, can enumerate natural drying, heat drying, drying under reduced pressure.Preferred heat drying.When above-mentioned the 1st functional layer was the situation of light diffusion layer, heating-up temperature was for example 60 ℃～150 ℃, and be for example 30 seconds～5 minutes heat time heating time.
Preferably in above-mentioned the 1st working procedure of coating, after above-mentioned coating and then comprise and make above-mentioned precursor polymeric.Polymerization can adopt suitable method arbitrarily according to the kind of resinous principle (being therefore its precursor).For example, when resinous principle is the situation of ionization ray solidified resin, make precursor polymeric by irradiation ionization property ray.When using the situation of ultraviolet ray conduct ionization property ray, its accumulative total light quantity is preferably 50mJ/cm 2～1000mJ/cm 2Ionization property ray is preferably more than 70% with respect to the transmitance of light diffusing particulate, and more preferably 80%.Again for example, when resinous principle is the situation of thermohardening type resin, make precursor polymeric by heating.Heating-up temperature and heat time heating time can suitably be set according to the kind of resinous principle.Preferred polymeric is undertaken by irradiation ionization property ray.If irradiation ionization property ray, because of when above-mentioned the 1st functional layer is the situation of light diffusion layer, can be in the situation that keep preferably the index modulation zone to make curing of coating, therefore can form the good light diffusion layer of diffusion property.By making precursor polymeric, form the matrix with index modulation zone and the constant zone of refractive index.
Above-mentioned polymerization can be carried out before above-mentioned drying, also can carry out after drying.
In above-mentioned the 1st working procedure of coating, except above-mentioned coating, drying and polymerization, can comprising arbitrarily at any reasonable time point, suitable operation, processing and/or operation be self-evident.The kind of this kind operation etc. and the time point that carries out this kind operation etc. can suitably be set according to purpose.
So form the 1st functional layer by the 1st working procedure of coating.In the 1st functional layer after above-mentioned the 1st working procedure of coating, on its surface, above-mentioned fluorine is that the levelling agent deflection exists.
B. the 2nd working procedure of coating
The 2nd working procedure of coating of manufacture method of the present invention forms the 2nd functional layer at the surface of the 1st functional layer that forms by above-mentioned the 1st working procedure of coating coating the 2nd coating liquid.The 2nd working procedure of coating comprises: be coated with the 2nd coating liquid and make the coated film that is formed at the 2nd coating liquid on the 1st functional layer dry on above-mentioned the 1st functional layer.When coating the 2nd coating liquid, above-mentioned fluorine is that levelling agent is that partially above-mentioned the 1st functional layer is surperficial.The 2nd functional layer for example can be anti-reflection layer.
Above-mentioned the 2nd coating liquid preferably comprises suitable resin or its precursor arbitrarily.For example, when the 2nd functional layer was the situation of anti-reflection layer, above-mentioned the 2nd coating liquid was preferably ultraviolet hardening acryl resin or its precursor or makes the mixed stocker materials of inorganic microparticle-dispersed in resin such as cataloid etc.
Above-mentioned the 2nd coating liquid preferably comprises volatile solvent.The volatile solvent that comprises in the 2nd coating liquid is preferably the higher solvent of levelling agent compatibility with above-mentioned fluorine, particularly, can enumerate methyl isobutyl ketone (MIBK) etc.If such volatile solvent, retrodeviating at above-mentioned the 1st working procedure of coating the above-mentioned fluorine that is the 1st functional layer surface is levelling agent, easily is eluted in the volatile solvent that the 2nd coating liquid comprises.
Above-mentioned fluorine be levelling agent as mentioned above, wash-out in the volatile solvent that comprises in the 2nd coating liquid moves to the 2nd coating liquid from the 1st functional layer.Manufacturing method according to the invention is because fluorine as mentioned above is that levelling agent does not have reactive group, therefore can easily move to the 2nd coating liquid.In addition, as the volatile solvent that comprises in the 2nd coating liquid as mentioned above, using with above-mentioned fluorine is the higher solvent of the compatibility of levelling agent, and to make thus fluorine be levelling agent becomes easier to the movement of the 2nd coating liquid.Manufacturing method according to the invention is that levelling agent is so mobile by fluorine, and this fluorine is the homogenization that levelling agent can be conducive to the thickness of the 1st functional layer, also can be conducive to the homogenization of the thickness of the 2nd functional layer.That is, can realize higher optics homogeneity.And then manufacturing method according to the invention and the blooming that obtains are that the amount of levelling agent is less because of the fluorine at the interface of the 1st functional layer and the 2nd functional layer, therefore excellent scratch resistance.
Above-mentioned fluorine is that levelling agent moves to the 2nd coating liquid as mentioned above, and then, the coated film surface deflection existence that forms at coating the 2nd coating liquid.Deflection exists if so, by the effect identical with the effect that illustrates in above-mentioned A item, obtains the 2nd functional layer of thickness and precision excellence.In addition, the blooming that autofrettage according to the present invention obtains is that the levelling agent deflection exists because fluorine is arranged in the 2nd functional layer surface, therefore excellent scratch resistance.
Above-mentioned the 2nd coating liquid also can and then contain suitable adjuvant arbitrarily according to purpose.For example, disperse well in order to make the ultra micron composition, can preferably use spreading agent.As other concrete examples of adjuvant, can enumerate ultraviolet light absorber, defoamer.
The solid component concentration of above-mentioned the 2nd coating liquid preferably can tune to about 10 % by weight～70 % by weight.If such solid component concentration can obtain to have the coating liquid of the viscosity of easy coating.
The coating process of above-mentioned the 1st coating liquid can be enumerated the method identical with the coating process of the 1st coating liquid that illustrates in above-mentioned A item.
As the drying means of above-mentioned the 2nd coating liquid, can adopt suitable method arbitrarily.As concrete example, can enumerate natural drying, heat drying, drying under reduced pressure.Preferred heat drying.When above-mentioned the 2nd functional layer was the situation of anti-reflection layer, heating-up temperature was for example 60 ℃～150 ℃, and be for example 30 seconds～5 minutes heat time heating time.
In above-mentioned the 2nd working procedure of coating, except above-mentioned coating and drying, comprising arbitrarily at any reasonable time point, suitable operation, processing and/or operation is self-evident.The kind of such operation etc. and the time point that carries out such operation etc. can suitably be set according to purpose.
So operation forms the 2nd functional layer by the 2nd working procedure of coating.After above-mentioned the 2nd working procedure of coating, on the surface of the 2nd functional layer, it is that the levelling agent deflection exists that above-mentioned fluorine is arranged.
Manufacture method of the present invention according to the purposes of blooming, can and then comprise other working procedure of coating, can and then form other functional layers.Other working procedure of coating can carry out before the 1st working procedure of coating, also can be after the 1st working procedure of coating, carry out before the 2nd working procedure of coating, in addition, also can carry out after the 2nd working procedure of coating.In other working procedure of coating, the solvent flashing that comprises in coating liquid is preferably the higher solvent of the compatibility of levelling agent with above-mentioned fluorine.Its reason is, fluorine is that levelling agent can move in the functional layer that forms by each working procedure of coating, can exist in the outermost surface deflection of blooming at last.
C. blooming
Figure 1A be for explanation according to a preferred embodiment of the invention manufacture method and the schematic diagram of the formation of the blooming that obtains, Figure 1B amplifies near light diffusion particulate with the 1st functional layer 120 (light diffusion layer) of Figure 1A and the schematic diagram that describes.Blooming 100 possesses base material film 110, the 1st functional layer 120 and the 2nd functional layer 130 successively.In the 2nd functional layer 130, it is levelling agent 10 that its surface (that is, in the 2nd functional layer 130 with the surface of the 1st functional layer 120 opposition sides) deflection has fluorine.In an embodiment, the 1st functional layer 120 is light diffusion layer, and the 2nd functional layer 130 is anti-reflection layer.Manufacturing method according to the invention and the blooming that obtains, because the brightness disproportionation of light diffusion layer and the interference inequality of anti-reflection layer are suppressed, and excellent scratch resistance, therefore be useful in for example being disposed at the most surperficial mode of liquid crystal indicator.
When above-mentioned the 1st functional layer 120 was the situation of light diffusion layer, as shown in Figure 1A, the 1st functional layer 120 preferably had matrix 20 and is dispersed in light diffusing particulate 30 in this matrix.Matrix 20 comprises resinous principle 21 and ultra micron composition 22.Above-mentioned light diffusion layer is that the refringence by matrix and light diffusing particulate shows light diffusion function.Preferably as shown in Figure 1A and Figure 1B, ultra micron composition 22 is to form the form in index modulation zone 40 with the near interface at matrix 20 and light diffusing particulate 30, disperses in resinous principle 21.Thereby matrix 20 has: with the index modulation zone 40 of the near interface of light diffusing particulate 30, and the constant zone of refractive index in the outside (away from a side of light diffusing particulate) in this index modulation zone 40.Preferably, matrix 20 is essentially refractive index constant zone except the part the index modulation zone.So-called " near interface of matrix and light diffusing particulate " comprises the outside of light diffusing microparticle surfaces, near surface and the inside of near surface in this manual.
Preferred above-mentioned light diffusion layer satisfies following formula (3) and (4):
Δn≥0.10 …(3)
0.0006≤Δn/L≤0.01 …(4)
Here, Δ n is the mean refractive index n of matrix MRefractive index n with the light diffusing particulate PThe absolute value of difference | n M-n P|, L is the average thickness in index modulation zone.The mean refractive index n of matrix MWeighted mean for the refractive index of the refractive index of resinous principle and ultra micron composition.Δ n is preferably more than 0.12.The upper limit of Δ n is preferably 0.20.If Δ n is lower than 0.10, turbidity situation about becoming below 90% is more, and its result when being assembled to the situation of liquid crystal indicator, can't make the light from light source fully spread, and the possibility that makes the visual angle become narrow is arranged.If Δ n surpasses 0.20, there is back scattering to become large possibility.In addition, the difficult resinous principle of matrix and the situation of ultra micron composition selected that become arranged.And then be preferably n M＞n PΔ n/L (nm -1) be preferably 0.0008～0.008, and then be preferably 0.0010～0.007.The average thickness L that can realize the index modulation zone of such Δ n/L is preferably 5nm～500nm, 12nm～400nm more preferably, and then be preferably 15nm～300nm.If average thickness L lower than 5nm, has back scattering to become large situation.If average thickness L surpasses 500nm, the inadequate situation of diffusivity is arranged.So, about above-mentioned light diffusion layer, although the average thickness L in index modulation zone is very thin, also can form larger (that is, Δ n/L is especially large) index modulation zone of Δ n.And as mentioned above, above-mentioned light diffusion layer can make refractive index change in fact continuously in the index modulation zone.By these synergy, can realize that turbidity value is higher, have the blooming of the film that strong diffusivity and back scattering be suppressed according to above-mentioned light diffusion layer.
As mentioned above, in index modulation zone 40, refractive index changes in fact continuously.Preferably in addition, the outermost refractive index in above-mentioned index modulation zone is identical in fact with the refractive index in above-mentioned refractive index constant zone.In other words, in above-mentioned light diffusion layer, refractive index changes continuously from the index modulation zone to refractive index constant zone, and constant zone changes (Fig. 2) to preferred index continuously from the light diffusing particulate to refractive index.Preferred this variations in refractive index is steady as shown in Figure 2.That is, on the border with the constant zone of refractive index, index modulation zone, change with the shape that can draw tangent line on the variations in refractive index curve.Preferably in the index modulation zone, the gradient of variations in refractive index is along with becoming large away from above-mentioned light diffusing particulate.According to above-mentioned light diffusion layer, as illustrated in above-mentioned A item, by suitably resinous principle and the ultra micron composition of selective light diffusivity particulate, matrix, can realize successional in fact variations in refractive index.Its result even increase the refringence of matrix 20 (be essentially refractive index constant zone) and light diffusing particulate 30, also can suppress the reflection at matrix 20 and the interface of light diffusing particulate 30, can suppress back scattering.And then, in the constant zone of refractive index, refractive index and light diffusing particulate 30 have the weight concentration of more different ultra micron composition 22 relatively to uprise, therefore can increase the refringence of matrix 20 (be essentially refractive index constant zone) and light diffusing particulate 30.Its result is even also can realize higher turbidity (stronger diffusivity) for film.Thereby, according to above-mentioned light diffusion layer, by forming the very large and refractive index of Δ n/L continually varying index modulation zone in fact, can realize high turbidity, and can significantly suppress back scattering.
Preferred above-mentioned light diffusion layer satisfies formula (5):
0.01≤L/r P≤1.0 …(5)
Here, r PRadius for above-mentioned light diffusing particulate.L/r PBe preferably 0.02～0.90.Because of by above-mentioned light diffusion layer, can make as mentioned above the average thickness L in index modulation zone very thin, therefore can make L/r PVery little.Its result can be kept the scattering power of above-mentioned light diffusing particulate fully, suppresses preferably back scattering.Thereby, even also can realize higher turbidity (stronger diffusivity) for film.
The thickness in above-mentioned index modulation zone 40 (the outermost distance in zone from index modulation zone penetralia to index modulation) can be constant (namely, the index modulation zone also can be with concentric spherical increase around the light diffusing particulate), thickness also can be with the position of light diffusing microparticle surfaces difference (for example also can become the flat sugared outer contour shape of gold such).The thickness in index modulation zone 40 is preferably different because of the position of light diffusing microparticle surfaces.If such structure in index modulation zone 40, can make refractive index change continuously more reposefully.Above-mentioned average thickness L is the thickness in index modulation zone 40 average thickness during because of the different situation in the position of light diffusing microparticle surfaces, during the situation of constant thickness, is this thickness.
As mentioned above, matrix 20 preferably comprises resinous principle 21 and ultra micron composition 22.Preferred above-mentioned index modulation zone 40 be based on the ultra micron composition 22 in matrix 20 dispersion concentration substantive gradient and form.Particularly, in index modulation zone 40, along with away from light diffusing particulate 30, the dispersion concentration of ultra micron composition 22 (representative is stipulated with weight concentration) uprises (the inevitable step-down of the weight concentration of resinous principle 21).In other words, in the zone of the adjacent light diffusivity particulate 30 in index modulation zone 40, ultra micron composition 22 is to disperse with relatively low concentration, and the concentration of ultra micron composition 22 is along with increasing away from light diffusing particulate 30.For example, through mode electron microscope (TEM, Transmission electron microscope) area ratio of the ultra micron composition 22 in the matrix 20 of image, a side at adjacent light diffusivity particulate 30 is less, a side at adjacent substrate 20 is larger, and this area ratio one side forms substantive gradient from light diffusing particulate side direction matrix side (the constant area side of refractive index) and simultaneously changes.The TEM image that represents the disperse state that it is representative is shown in Fig. 3.In this manual, so-called " area ratio of the ultra micron composition in the matrix of through mode electron microscope image ", refer in the through mode electron microscope image of the section of the diameter that comprises the light diffusing particulate the shared area ratio of ultra micron composition in the matrix of specialized range (regulation area).This area ratio is corresponding with the dispersion concentration (actual dispersion concentration) of the three-dimensional of ultra micron composition.For example, if area ratio as above, the dispersion concentration of ultra micron composition 22, the gradient of its concentration change is less in a side of adjacent light diffusivity particulate 30, a side in contiguous refractive index constant zone is larger, and one side forms substantive gradient from the constant area side of light diffusion particulate lateral refractive index and simultaneously changes.In other words, the dispersion concentration of ultra micron composition 22 is: the gradient of its concentration change is along with becoming large away from the light diffusing particulate.The area ratio of this ultra micron composition can utilize any suitable image analysis software to try to achieve.Need to prove, what above-mentioned area ratio was representative is corresponding with each interparticle average bee-line of ultra micron composition.Particularly, the interparticle average bee-line of each of ultra micron composition in the index modulation zone along with shortening away from the light diffusing particulate, become in refractive index constant zone constant (for example, average bee-line is 3nm～100nm left and right in the zone of adjacent light diffusivity particulate, is 1nm～20nm) in refractive index constant zone.Average bee-line is the TEM image binaryzation with as shown in Figure 3 disperse state, for example can use the center of gravity spacing method of image analysis software " A is as く ん " (Engineering company of Asahi Chemical Industry system) to calculate.As mentioned above, according to above-mentioned light diffusion layer, can utilize the substantive gradient of the dispersion concentration of ultra micron composition 22, form index modulation zone 40 at the near interface of matrix and light diffusing particulate, therefore can form light diffusion layer with easy step and especially low cost.And then the substantive gradient of the dispersion concentration by utilizing the ultra micron composition forms the index modulation zone, and refractive index 40 is changed with the border in refractive index constant zone reposefully in the index modulation zone.And then, by using refractive index and resinous principle and light diffusing particulate that more different ultra micron composition is arranged, can increase the refringence of light diffusing particulate and matrix (be essentially refractive index constant zone) and make the refractive index gradient in index modulation zone precipitous.
As mentioned above, in above-mentioned light diffusion layer, be preferably n M＞n PAs shown in being compared in Fig. 4 (a) and Fig. 4 (b), n M＞n PSituation and n M＜n PSituation compare, even the refractive index gradient in index modulation zone is precipitous, also can suppress better back scattering.
Manufacturing method according to the invention and the thickness of the blooming that obtains can be set as suitable value arbitrarily according to purposes.
The thickness of above-mentioned the 1st functional layer can be set as suitable value arbitrarily according to purposes.When above-mentioned the 1st functional layer was the situation of light diffusion layer, the thickness of this light diffusion layer was preferably 4 μ m～50 μ m, and then was preferably 4 μ m～20 μ m, was particularly preferably 5 μ m～15 μ m.The light diffusion layer that can form according to above-mentioned manufacture method is although so very thin of thickness also has very high turbidity as above.And then, if having the blooming of the light diffusion layer of such thinner thickness, even if bending can not broken yet, can take care of with drum.Therefore in addition, because blooming of the present invention can form by coating, for example can utilize so-called volume to volume to carry out continuously the manufacturing of blooming and to the applying of other members (for example, the polarization plates of liquid crystal indicator).Therefore, manufacture method of the present invention productivity compared with the past is especially excellent, and is also high to the manufacturing efficient of the applying of other optical components as polarization plates.Need to prove, so-called volume to volume refer to the strip film each other one side by the roller conveyance, the one side method that its length direction is fitted continuously of aliging.
The blooming that manufacturing method according to the invention obtains, thickness and precision is excellent as mentioned above.When above-mentioned the 1st functional layer is the situation of light diffusion layer, the thickness and precision of this light diffusion layer is in the size of 100mm * 100mm, be preferably (average thickness-1.0 μ m)～(average thickness+1.0 μ m) more preferably (average thickness-0.5 μ m)～(average thickness+0.5 μ m).If such scope even be set as greatlyr in the refringence with matrix and light diffusing particulate, during situation that the outward appearance of light diffusion layer bleaches, also can obtain the uneven less light diffusion layer of outward appearance.Need to prove, the degree of the optics homogeneity of light diffusion layer, for example can form according to the mode with this light diffusion layer of clamping with to intersect the duplexer of 2 polarization plates of state configuration of Niccol, the variable quantity (standard deviation) of brightness and quantizing in the face of outgoing plane when white light is seen through from a face of this duplexer.The standard deviation of brightness is preferably below 1 in this face, more preferably below 0.8, and then is preferably 0.1～0.7.
When above-mentioned the 1st functional layer was the situation of light diffusion layer, what the diffusion property of this light diffusion layer was representative was to represent by turbidity and light diffusion half-value angle.So-called turbidity means the intensity of the diffusion of light, the i.e. diffusion of incident light.On the other hand, so-called light diffusion half-value angle means the quality of diffusion light, the i.e. angular range of the light of diffusion.The turbidity value of this light diffusion layer is more than 75%, is preferably 75%～99.9%, more preferably 85%～99.9%, and then be preferably 90%～99.9%, be particularly preferably 95%～999%.
If the diffusion property of above-mentioned light diffusion layer represents with light diffusion half-value angle, be preferably 10 °～150 ° (one-sided 5 °～75 °), more preferably 10 °～100 ° (one-sided 5 °～50 °), and then be preferably 30 °～80 ° (one-sided 15 °～40 °).If light diffusion half-value angle is too small, the situation that has oblique visual angle (for example white brightness) to narrow down.If light diffusion half-value angle is excessive, there is back scattering to become large situation.
When above-mentioned the 2nd functional layer is the situation of anti-reflection layer, the thickness and precision of this anti-reflection layer is in the size of 100mm * 100mm, be preferably (average thickness-2.0nm)～(average thickness+2.0nm), more preferably (average thickness-1.8nm)～(average thickness+1.8nm), and then be preferably (average thickness-1.7nm)～(average thickness+1.7nm).Need to prove, the optics homogeneity of anti-reflection layer can be estimated qualitatively by for example interference fringe.
The thickness of above-mentioned the 2nd functional layer can be set as suitable value arbitrarily according to purposes.When above-mentioned the 2nd functional layer was the situation of anti-reflection layer, the thickness of this anti-reflection layer was preferably 70nm～100nm.
When above-mentioned the 2nd functional layer was the situation of anti-reflection layer, the refractive index of this anti-reflection layer can be set as according to the thickness of anti-reflection layer suitable value arbitrarily.Preferred 1.38～1.51.
[embodiment]
Below, illustrate the present invention by embodiment, but the present invention is not limited to these embodiment.The evaluation method of embodiment is as described below.In addition, as long as mark especially, " part " in embodiment to reach " % " be weight basis.
(1) mar resistance
The 2nd functional layer for the blooming that obtains in embodiment and comparative example is surperficial, steel wool (steel wool) (#0000) is come and gone 10 times under load 300g, on Visual Confirmation blooming at this moment, not damaged is arranged, and estimate according to following benchmark.
A ... without obviously damage
B ... as seen 1～7 damage
C ... as seen damage in a large number
The surface free energy of (2) the 2nd functional layers
The blooming damping under 25 ℃ of temperature, humidity 60%RH that obtains in embodiment and comparative example after 2 hours, is measured it to the contact angle of water, calculate surface free energy by these values.
(3) the optics homogeneity of blooming
(3-1) brightness disproportionation of blooming
Use clear binder, form blooming, polarization plates and the glass plate (thickness: duplexer 0.7mm) (glass plate/polarization plates/glass plate/blooming/polarization plates/glass plate) that obtains in embodiment and comparative example.At this moment, 2 polarization plates are that to intersect the state of Niccol stacked.Use high brightness White LED backlight, make white light see through this duplexer.For the outgoing plane that sees through light use the brightness measuring camera (CYBERNET company makes, trade name " PROMETRIC1600 ", photographic images is with brightness number datumization in face.
Remove the bright spot part in the face of gained in brightness value, and revise the fluctuating in the cycle larger than the cycle of outward appearance inequality, and calculate the standard deviation of brightness 1Standard deviation according to this brightness 1, the brightness disproportionation (being more specifically the brightness disproportionation of the 1st functional layer) of evaluation blooming.
(3-2) thickness and precision of the 2nd functional layer
On the blooming that obtains in embodiment and comparative example, the trade name " MCPD2000 " of utilizing large tomb electronics corporation to make is measured respectively the thickness of 10 of random selection, is calculated the standard deviation of the thickness of the 2nd functional layer by this measured value 2
(4) fluorine is the distribution 1 of levelling agent
For the blooming that obtains in embodiment 1 and comparative example 1, use time of flight secondary ion massspectrometry instrument (TOF-SIMS, Time-of-Flight Secondary Ion Mass Spectrometry) (ION-TOF company makes, trade name " TOF-SIMS5 "), measure the distribution of the fluorine ion intensity of blooming section (the 2nd functional layer surface～degree of depth 270nm).
(5) fluorine is the distribution 2 of levelling agent
The atom ratio of the atom (F, C, N, O, Al, Si, Zr) for the 2nd functional layer surface of the blooming that obtains in embodiment 1 to the scope of degree of depth 270nm, the trade name " Quantum2000 " that use ULVAC-PHI company makes is carried out ESCA (electron spectroscopy for chemical analysis, electron spectroscopy for chemical analysis) and is analyzed.
(6) the thickness L in index modulation zone
The blooming one side that obtains in embodiment and comparative example is cooling in liquid nitrogen, and it is the thickness of 0.1 μ m that one side is utilized the microtome section, makes the mensuration test portion.Utilize through mode electron microscope (TEM) to observe the state at the interface of the state of particulate of the 1st functional layer (light diffusion layer) part of this mensuration test portion and this particulate and matrix, the unclear part in interface of assert particulate and matrix is the index modulation zone, uses image analysis software to calculate its average thickness L from the TEM image.More specifically, be chosen in the maximum particulate in the scope of observing in the sectional tem image of the wide visual field (300 times of multiplying powers), utilize image analysis software to calculate the thickness of observing in the enlarged image at the interface of selected particulate and matrix (12000 times of multiplying powers).Carry out this analysis at any 5 places, with the thickness of its average thickness as the index modulation zone.The interface of particulate and matrix clearly situation is regarded as and is not formed the index modulation zone.
(7) light diffusion half-value angle
the blooming that obtains from embodiment and comparative example is peeled off base material film and the 2nd functional layer and is obtained the 1st functional layer (light diffusion layer), front illuminated laser light from gained the 1st functional layer (light diffusion layer), use goniophotometer (goniophotometer) to measure the light of diffusion with respect to the diffusion brightness of diffusion angle every 1 °, as shown in Figure 5, measure brightness in the both sides of diffusion from advance the diffusion angle that becomes a half intensity through the maximal value of the diffusion of the light light brightness except laser straight, (angle A+angle A of Fig. 5 ') that satisfies the angle of these both sides is made as light diffusion half-value angle.
(8) Backward Scattering Ratio
Similarly obtain the 1st functional layer (light diffusion layer) with above-mentioned (7), by clear binder, the 1st functional layer is fitted in (the sumitomo chemical company manufacturing of black acrylic plate, trade name " SUMIPEX " (registered trademark), thickness 2mm) on, make the mensuration test portion.Utilize a minute luminometer (tester company of Hitachi makes, trade name " U4100 ") to measure the integrated reflectivity of this mensuration test portion.On the other hand, the coating liquid of use after the 1st functional layer (light diffusion layer) formation is removed particulate with coating liquid, make the duplexer of base material and transparent overlay and test portion in contrast, with the above-mentioned integrated reflectivity (being surface reflectivity) of similarly measuring.The integrated reflectivity (surface reflectivity) that deducts above-mentioned contrast test portion by the integrated reflectivity from the said determination test portion is calculated the Backward Scattering Ratio of the 1st functional layer (light diffusion layer).
＜embodiment 1 〉
at zirconium oxide nano-particle (the mean grain size 60nm as the ultra micron composition that contains 62%, average primary particle diameter 10nm, refractive index 2.19) be coated with firmly that (JSR company makes with resin, trade name " Opstar KZ6661 " (containing MEK/MIBK)) in 100 parts, interpolation is as pentaerythritol triacrylate (Osaka organic chemistry industrial group manufacturing of the precursor of resinous principle, trade name " Biscoat#300 ", refractive index 1.52) 11 parts of 50% methyl ethyl ketone (MEK) solution, (BASF Japan company makes Photoepolymerizationinitiater initiater, trade name " Irgacure907 ") 0.5 part, (ponding changes into product industrial groups and makes as polymethylmethacrylate (PMMA) particulate of light diffusing particulate, trade name " XX-131AA ", mean grain size 2.5 μ m, refractive index 1.495) 15 parts, and the fluorine that does not have a reactive group is that (DIC company makes levelling agent, trade name " MEGAFAC TF-1661 ") be 0.5% with respect to above-mentioned whole solid state components.Use stirring machine (shallow field ironworker incorporated company, trade name " DESPA ") to carry out dispersion treatment to this potpourri, prepare the 1st functional layer (light diffusion layer) the formation coating liquid that above-mentioned each uniform component is disperseed.The solid component concentration that the 1st functional layer (light diffusion layer) forms with coating liquid is 55%.After preparation the 1st functional layer (light diffusion layer) forms with coating liquid, use at once rod to be coated with machine and it is coated in has TAC film (tri cellulose acetate membrane) that (Fuji Photo Film Co., Ltd. makes, trade name " Fujitac ", thickness 40 μ m) on base material film, after under 100 ℃ dry 1 minute, the ultraviolet ray of irradiation accumulative total light quantity 300mJ, the 1st functional layer (light diffusion layer) of formation thickness 10 μ m.
(JSR company makes will to contain many cyclopropylene acid esters of nano silicon (refractive index 1.49), trade name " KZ7540 ") 1.8% MIBK soln using rod is coated with on the 1st functional layer (light diffusion layer) that machine is coated on above-mentioned acquisition, after under 100 ℃ dry 1 minute, the ultraviolet ray of irradiation accumulative total light quantity 300mJ, the 2nd functional layer (anti-reflection layer) of formation thickness 110nm.
The blooming that acquisition like this has base material film (40 μ m)/the 1st functional layer (10 μ m)/the 2nd functional layer (110nm).
The blooming that obtains is supplied in the evaluation of above-mentioned (1)～(3).Show the result in table 1.In addition, be the distribution of levelling agent about fluorine in blooming, for reach the evaluation of (5) in above-mentioned (4).The Fig. 6 that the results are shown in of (4) will be estimated, the Fig. 7 that the results are shown in of (5) will be estimated.Need to prove, in Fig. 6, the deep or light expression fluorine ion intensity of color, color lighter (near white) fluorine ion intensity is stronger, represents that namely fluorine is that the amount of levelling agent is more.In addition, put down in writing fluorine atom (F) with respect to the atom ratio of the total of F, C, N, O, Al, Si and Zr in Fig. 7.
Need to prove, in table 1, the characteristic of the 1st functional layer (light diffusion layer) of record is not as follows: L=50nm, Δ n=0.12, Δ n/L=0.0024, light diffusion half-value angle=60 °, L/r P=0.04, Backward Scattering Ratio=0.38%.And then, carried out the structure again of three-dimensional image by the TEM image of the near interface part of the matrix of the 1st functional layer (light diffusion layer) and light diffusing particulate, should three-dimensional build again as binaryzation and carry out image and process, calculate apart from the distance of light diffusing microparticle surfaces and the relation of the dispersion concentration (having ratio) of ultra micron composition.Results verification is formed with the gradient of the dispersion concentration of ultra micron composition.
＜embodiment 2 〉
The addition that except the fluorine that will not have reactive group is levelling agent (DIC company make, trade name " MEGAFAC TF-1661 ") changes into beyond 0.2% from 0.5%, obtains similarly to Example 1 blooming.The blooming that obtains is supplied in the evaluation of above-mentioned (1)～(3).Show the result in table 1.
Need to prove, in table 1, the characteristic of the 1st functional layer (light diffusion layer) of record is not as follows: L=50nm, Δ n=0.12, Δ n/L=0.0024, light diffusion half-value angle=60 °, L/r P=0.04, Backward Scattering Ratio=0.38%.
＜comparative example 1 〉
The fluorine that has an isocyanate group except use is that (DIC company makes levelling agent, trade name " MEGAFAC RS-721 ": have the represented structural unit of above-mentioned general formula (I)～(III)) fluorine that replaces not having reactive group is that (DIC company makes levelling agent, trade name " MEGAFAC TF-1661 ") in addition, obtain similarly to Example 1 blooming.
The blooming that obtains is supplied in the evaluation of above-mentioned (1)～(3).Show the result in table 1.In addition, be the distribution of levelling agent about the fluorine of blooming, in the evaluation of above-mentioned (4).Show the result in Fig. 6.
Need to prove, in table 1, the characteristic of the 1st functional layer (light diffusion layer) of record is not as follows: L=49nm, Δ n=0.12, Δ n/L=0.0024, light diffusion half-value angle=60 °, L/r P=0.04, Backward Scattering Ratio=0.37%.
＜comparative example 2 〉
The fluorine that has an isocyanate group except use is that (DIC company makes levelling agent, trade name " MEGAFAC F479 ": do not have the represented structural unit of above-mentioned general formula (I)～(III)) fluorine that replaces not having reactive group is that (DIC company makes levelling agent, trade name " MEGAFAC TF-1661 ") in addition, obtain similarly to Example 1 blooming.
The blooming that obtains is supplied in the evaluation of above-mentioned (1)～(3).Show the result in table 1.
Need to prove, in table 1, the characteristic of the 1st functional layer (light diffusion layer) of record is not as follows: L=50nm, Δ n=0.12, Δ n/L=0.0024, light diffusion half-value angle=60 °, L/r P=0.04, Backward Scattering Ratio=0.39%.
[table 1]
Figure BDA00002939928600251
Manufacturing method according to the invention, as shown in Fig. 6 and 7, fluorine is that levelling agent is that partially the 2nd functional layer is surperficial.The surface free energy of the 2nd functional layer is that the fluorine on the 2nd functional layer surface is the index of the amount of levelling agent.Embodiment 1 and 2 blooming, surface free energy as shown in table 1 is less, learns that fluorine is that levelling agent is the 2nd functional layer surface partially.Such blooming mar resistance and optics homogeneity (reduce brightness disproportionation and interfere uneven) with excellence as shown in table 1.On the other hand, when the fluorine that has a reactive group in use is the situation of levelling agent, this fluorine be levelling agent as shown in Figure 6, the amount in the 2nd functional layer is considerably less.Such blooming is as shown in table 1, the thickness and precision of the 2nd functional layer relatively poor (the interference inequality is stronger).And then the blooming of comparative example 1 is because the fluorine at the interface of the 1st functional layer and the 2nd functional layer is that the amount of levelling agent is more, so mar resistance is relatively poor.Think that fluorine is levelling agent in the situation that partially be not to disperse in the 1st functional layer and the 2nd functional layer in the blooming of comparative example 2.Its result is, the thickness and precision of the 1st functional layer and the 2nd functional layer is relatively poor, and the optics homogeneity of blooming as shown in table 1 is low.In addition, the blooming of comparative example 2 is because fluorine is the interface that levelling agent residues in the 1st functional layer and the 2nd functional layer, so mar resistance is relatively poor.
[utilizability on industry]
By the blooming that manufacture method of the present invention obtains, can be preferably used for looking of liquid crystal indicator and recognize the backlight of side member, liquid crystal indicator and use pervasion component with member, ligthing paraphernalia (for example organic EL, LED).
[main element symbol description]
10 fluorine are levelling agent
20 matrix
21 resinous principles
22 ultra micron compositions
30 light diffusing particulates
40 index modulation are regional
100 bloomings
110 base material films
120 the 1st functional layers
130 the 2nd functional layers

Claims (10)

1. the manufacture method of a blooming, it comprises:
Face coating of base material film contain the fluorine with reactive group be the 1st coating liquid of levelling agent and form the 1st functional layer the 1st applying step, and
Form the 2nd applying step of the 2nd functional layer at the surface of the 1st functional layer coating the 2nd coating liquid,
With regard to this fluorine is levelling agent,
Be that partially the 1st functional layer is surperficial when coating the 2nd coating liquid, and be eluted to the 2nd coating liquid after coating the 2nd coating liquid in, and be that partially formed the 2nd functional layer is surperficial.
2. the manufacture method of blooming as claimed in claim 1, wherein,
Described fluorine is that levelling agent contains freely at least a kind of structural unit in the group that forms of the represented structural unit of represented structural unit, the following general formula (II) of following general formula (I) and the represented structural unit of following general formula (III) of choosing,
[changing 1]
Figure FDA00002939928500011
-O-CF 2-O- …(III)
In general formula (I), m is 1～10 integer, and in general formula (II), n is 2～10 integer.
3. the manufacture method of blooming as claimed in claim 1 or 2, wherein,
Described fluorine is that the content of levelling agent is 0.05 % by weight～3 % by weight with respect to the whole solid state components in described the 1st coating liquid.
4. as the manufacture method of the described blooming of any one in claim 1～3, wherein,
Described the 1st functional layer is light diffusion layer.
5. as the manufacture method of the described blooming of any one in claim 1～4, wherein,
Described the 2nd functional layer is anti-reflection layer.
6. as the manufacture method of claim 4 or 5 described bloomings, wherein,
Described light diffusion layer has matrix and the light diffusing particulate that is dispersed in this matrix,
Near the interface of this matrix and this light diffusing particulate or its, be formed with the index modulation zone that refractive index changes in fact continuously, and satisfy following formula (3) and (4),
Δn≥0.10 …(3)
0.0006≤Δn/L≤0.01 …(4)
Here, Δ n is the mean refractive index n of matrix MRefractive index n with the light diffusing particulate PThe absolute value of difference | n M-n P|, L is the average thickness in index modulation zone.
7. the manufacture method of blooming as claimed in claim 6, wherein,
n M＞n P。
8. as the manufacture method of claim 6 or 7 described bloomings, wherein,
Described light diffusion layer satisfies formula (5),
0.01≤L/rP≤1.0 …(5)
Here, r PRadius for described light diffusing particulate.
9. as the manufacture method of the described blooming of any one in claim 6～8, wherein,
Described matrix contains resinous principle and ultra micron composition, and the substantive gradient that described index modulation zone is based on the dispersion concentration of this ultra micron composition in this matrix forms.
10. the manufacture method of blooming as claimed in claim 9, wherein,
Described light diffusion layer satisfies formula (1),
|n P-n A|＜|n P-n B| …(1)
Here, n AThe refractive index of the resinous principle of expression matrix, n BThe refractive index of the ultra micron composition of expression matrix.
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