CN102356335B - Process for producing light-diffusing element, light-diffusing element, and processes for producing polarizing plate with light-diffusing element and liquid-crystal display device - Google Patents

Process for producing light-diffusing element, light-diffusing element, and processes for producing polarizing plate with light-diffusing element and liquid-crystal display device Download PDF

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CN102356335B
CN102356335B CN2010800125331A CN201080012533A CN102356335B CN 102356335 B CN102356335 B CN 102356335B CN 2010800125331 A CN2010800125331 A CN 2010800125331A CN 201080012533 A CN201080012533 A CN 201080012533A CN 102356335 B CN102356335 B CN 102356335B
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light
light diffusing
diffusion element
diffusing particulate
light diffusion
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CN102356335A (en
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渊田岳仁
武本博之
首藤俊介
宫武稔
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Nitto Denko Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00663—Production of light guides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00798—Producing diffusers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Abstract

A process for producing a light-diffusing element is provided by which a light-diffusing element having a high haze and high diffusing properties and reduced in backward scattering can be produced at low cost with high productivity. The process for producing a light-diffusing element comprises a step in which a matrix-forming material comprising a resin-ingredient precursor and an ultrafine-particle ingredient is brought into contact with fine light-diffusing particles, a step in which at least some of the precursor is infiltrated into an inner part of the fine light-diffusing particles, and a step in which the precursor that has infiltrated into the inner part of the fine light-diffusing particles and the precursor that has not infiltrated into the fine light-diffusing particles are simultaneously polymerized to form a matrix comprising the resin ingredient and the ultrafine-particle ingredient and simultaneously form a concentration gradation region in the vicinity of the inner side of the surface of the fine light-diffusing particles.

Description

The manufacture method of light diffusion element, light diffusion element, with the polarization plates of light diffusion element and the manufacture method of liquid crystal indicator
Technical field
The present invention relates to the manufacture method, light diffusion element of light diffusion element and with the polarization plates of light diffusion element and the manufacture method of liquid crystal indicator.
Background technology
Light diffusion element just is being widely used in screen, surface illuminating device (such as liquid crystal indicator) of illuminating lamp shade, rear-projection TV etc.In recent years, light diffusion element advances in the utilization that improves the display quality of liquid crystal indicator etc., improve the aspects such as viewing angle characteristic.As light diffusion element, (for example with reference to patent documentations 1) such as elements that microparticulate is formed proposed in the matrix such as resin sheet.In such light diffusion element, the major part of the light of institute's incident is (exit facet side) scattering forwards, and some is (plane of incidence side) scattering rearward.The larger diffusivity of the refringence of particulate and matrix (for example haze value) is larger, but then, if more backscattering meeting increase of refringence.If backscattering is larger, when light diffusion element is used for liquid crystal indicator, when incidence of external light during to liquid crystal indicator picture can become and turn white, therefore be difficult to show image or the image with contrast.
As solution to the problems described above, based on the conception of the reflection on the interface that suppresses particulate and matrix, the core-shell particle (core-shell particle) that has proposed to make core different from the refractive index of shell or refractive index are from the central part of particulate continually varying what is called GRIN (gradient index: the gradient index) method (for example with reference to patent documentation 2～4) of particulate constant gradient refractive index microparticulate in resin laterally.Yet these particulates are compared with common particulate, and manufacturing process is comparatively complicated, so throughput rate is insufficient and do not have a practicality.
The prior art document
Patent documentation
Patent documentation 1: No. the 3071538th, Jap.P.
Patent documentation 2: Japanese patent laid-open 6-347617 communique
Patent documentation 3: Japanese Patent Laid-Open 2003-262710 communique
Patent documentation 4: Japanese Patent Laid-Open 2002-212245 communique
Summary of the invention
The present invention is the invention of completing for solving above-mentioned previous problem, and its purpose is, provide a kind of can low cost and high productivity ground make haze value high, have strong diffusivity and suppress the manufacture method of the light diffusion element of backscattered light diffusion element.
For the technological means of dealing with problems
The manufacture method of light diffusion element of the present invention comprises following operation: make the matrix of the precursor that contains resinous principle and ultra micron composition form material and the contacted operation of light diffusing particulate; Make at least a portion of this precursor infiltrate into the operation of the inside of this light diffusing particulate; And polymerization occurs and forms the matrix that contains resinous principle and ultra micron composition in precursor simultaneously that make the precursor of the inside that infiltrates into this light diffusing particulate and do not infiltrate into this light diffusing particulate, and simultaneously in the inner operation that forms the concentration adjustment district of the near surface of this light diffusing particulate.
In preferred embodiment, above-mentioned manufacture method is in above-mentioned infiltration operation, makes above-mentioned precursor infiltrate into more than 10% till the scope below 95% of mean grain size of this light diffusing particulate from the surface of above-mentioned light diffusing particulate.
In preferred embodiment, above-mentioned manufacture method makes the longer time of time till the particle diameter of the precursor of above-mentioned resinous principle and the above-mentioned light diffusing particulate of this light diffusing particulate contact gear ratio reaches in fact maximum.
In preferred embodiment, above-mentioned resinous principle is ionization ray solidified resin, and above-mentioned manufacture method makes the precursor generation polymerization of this resinous principle by irradiation ionization property ray.
According to a further aspect in the invention, provide a kind of light diffusion element.This light diffusion element obtains by above-mentioned method, have the matrix that contains resinous principle and ultra micron composition and be scattered in light diffusing particulate in this matrix, and have in the near surface inside of this light diffusing particulate the concentration adjustment district that this resinous principle forms through infiltration.
According to of the present invention and then on the other hand, provide a kind of manufacture method of the polarization plates with light diffusion element.Use the manufacture method of above-mentioned light diffusion element in the method.
According to of the present invention and then on the other hand, provide a kind of manufacture method of liquid crystal indicator.Use the manufacture method of above-mentioned light diffusion element in the method.
The effect of invention
According to the present invention, when being used in combination specific matrix resin composition (being essentially its precursor) and making light diffusion element with specific light diffusing particulate, can make the precursor infiltration of matrix resin composition inner to the light diffusing particulate.Can form matrix by making this precursor generation polymerization, and simultaneously in the inner concentration adjustment district (that is, (one batch) forms matrix and concentration adjustment district once) that forms of the near surface of this light diffusing particulate.So, according to the present invention, need not to carry out special processing, operation for forming the concentration adjustment district, therefore can low cost and high productivity ground make light diffusion element.And, the light diffusion element that obtains by manufacture method of the present invention, be formed with the concentration adjustment district in the near surface inside of light diffusing particulate, therefore can make at the near interface of light diffusing element and matrix refractive index interimly or change to continuity in fact.Therefore, can control well the reflection at the interface of matrix and light diffusing particulate, thereby can suppress backscattering.In addition, according to the present invention, have by use the specific phase dissolubility of ultra micron composition specific refractive index reaches to(for) resinous principle, can easily adjust the refractive index of matrix.Particularly according to the present invention, can improve the concentration of the ultra micron composition in matrix by making resinous principle infiltrate into light diffusing particulate inside, therefore can easily enlarge the refringence of matrix and light diffusing particulate.Its result is, the haze value of the light diffusion element that obtains by manufacture method of the present invention is higher, has strong diffusivity, and has suppressed backscattering.
Description of drawings
Fig. 1 is the mode chart of the disperse state of the resinous principle of the light diffusion element mesostroma that obtains for the manufacture method of explanation by the preferred embodiment of the present invention and light diffusing particulate;
Fig. 2 (a) is for the concept map that light diffusion element of the present invention variations in refractive index till the matrix from light diffusing particulate central part is described, Fig. 2 (b) is for the concept map that previous light diffusion element variations in refractive index till the matrix from the particulate central part is described;
Fig. 3 means about the different coating liquid of time of repose, the curve map of baking temperature and the relation of the diffusion half-power angle that obtains;
Fig. 4 is the summary section with the polarization plates of light diffusion element that the manufacture method by the preferred embodiment of the present invention obtains;
Fig. 5 is the summary section of the liquid crystal indicator that obtains of the manufacture method by the preferred embodiment of the present invention;
Fig. 6 calculates the mode chart of the method for light diffusion half-power angle for explanation;
Fig. 7 means the transmission electron microscope photo about the concentration adjustment district of embodiment 1,3 and 4 light diffusion element.
Embodiment
Below, one side is with reference to accompanying drawing, and one side is illustrated with regard to the preferred embodiment of the present invention, but the present invention is not limited to these embodiments.
A. the manufacture method of light diffusion element
The manufacture method of light diffusion element of the present invention comprises following operation: make the matrix of the precursor that contains resinous principle and ultra micron composition form material and the contacted operation of light diffusing particulate (being made as operation A); Make at least a portion of this precursor infiltrate into the operation (being made as process B) of the inside of this light diffusing particulate; And make this precursor generation polymerization and form the matrix that contains resinous principle and ultra micron composition, and simultaneously in the inner operation (being made as operation C) that forms the concentration adjustment district of the near surface of this light diffusing particulate.
A-1. operation A
In operation A, representative is the preparation coating liquid, and the precursor that the making of this coating liquid contained resinous principle and the matrix of ultra micron composition form material and light diffusing particle dissolution or is scattered in the solution that forms in volatile solvent.Representatively be that this coating liquid is the dispersion that ultra micron composition and light diffusing microparticulate are formed in precursor and volatile solvent.As the method that makes ultra micron composition and light diffusing microparticulate, can adopt suitable method (for example ultrasound wave processing) arbitrarily.In this coating liquid, the light diffusing particulate contacts with the precursor of resinous principle.
A-1-1. resinous principle
As long as above-mentioned resinous principle can form above-mentioned concentration adjustment district well, just can contain suitable material arbitrarily.The refractive index of resinous principle satisfies the relation of following formula (1):
0＜|n P-n A|···(1)
In formula (1), n AThe refractive index of the resinous principle of expression matrix, n PThe refractive index of expression light diffusing particulate.| n P-n A| be preferably 0.01～0.10, more preferably 0.01～0.06, be particularly preferably 0.02～0.06.If | n P-n A| do not reach 0.01, have the situation that does not form above-mentioned concentration adjustment district.If | n P-n A| surpass 0.10, might backscattering increase.
It is the compound of homology that resinous principle preferably contains with the light diffusing particulate.More preferably to contain with the light diffusing particulate be the compound that in the compound of homology, intermiscibility is higher to resinous principle.Thus, resinous principle is because being the material with light diffusing particulate homology, thus its precursor (monomer) to be permeable to the light diffusing particulate inner.Polymerization occurs by polymerization process described later in this precursor (monomer), and its result can utilize resinous principle to form well the concentration adjustment district in the near surface inside of light diffusing particulate.Moreover, in this instructions so-called " homology ", refer to chemical constitution, characteristic is equal or similar, so-called " not homology " refers to the situation beyond homology.Whether be homology, can be different because of the system of selection of benchmark.For example, when the situation take organic or inorganic as benchmark, organic compound gang is the compound of homology, and organic compound and mineral compound are the compound of homology not.When the situation take the repetitive of polymkeric substance as benchmark, though for example acrylic acid series polymeric compounds and epoxy based polymer are organic compound gang, but still be the compound of homology not, when the situation take the periodic table of elements as benchmark, though alkaline metal and transition metal are inorganic elements gang, but still it is the element of homology not.
Above-mentioned resinous principle preferably contains organic compound, more preferably contains ionization ray solidified resin.The hardness of film of ionization ray solidified resin is excellent.As ionization property ray, can enumerate for example ultraviolet ray, visible light, infrared ray, electron beam.Take ultraviolet ray as preferred, so resinous principle particularly preferably contains ultraviolet curing resin.As ultraviolet curing resin, can enumerate such as the radical polymerization mould assembly monomers such as acrylate resin (epoxy acrylate, polyester acrylate, acrylic acid propylene, ether acrylate) or oligomer etc.The molecular weight that consists of the monomer component (precursor) of acrylate resin is preferably 200～700.As the concrete example of the monomer component (precursor) that consists of acrylate resin, can enumerate pentaerythritol triacrylate (PETA: molecular weight is 298), neopentylglycol diacrylate (NPGDA: molecular weight is 212), dipentaerythritol acrylate (DPHA: molecular weight is 632), dipentaerythritol five acrylate (DPPA: molecular weight is 578), trimethylolpropane triacrylate (TMPTA: molecular weight is 296).Such monomer component (precursor) has molecular weight and the spatial structure of the cross-linked structure (tridimensional network) that is suitable for infiltrating into the light diffusing particulate, and is therefore preferred.Also can add as required initiating agent.As initiating agent, can enumerate such as UV free-radical generating agent (Irgacure907, the Irgacure 127 that Ciba (Ciba Specialty Chemicals) company makes, Irgacure 192 etc.), benzoyl peroxide.Above-mentioned resinous principle also can contain other resinous principle except containing above-mentioned ionization ray solidified resin.Other resinous principle can be ionization ray solidified resin, also can be heat-curing resin, also can be thermoplastic resin.As the typical example of other resinous principle, can enumerate fatty family (for example polyolefin) resin, polyurethane series resin.When using the situation of other resinous principle, its kind or allotment amount are adjusted, so that form well above-mentioned concentration adjustment district, and refractive index satisfies the relation of above-mentioned formula (1).
The refractive index of above-mentioned resinous principle is preferably 1.40～1.60.
With respect to formed matrix 100 weight portions, the allotment amount of the above-mentioned resinous principle in above-mentioned coating liquid is preferably 20 weight portions～80 weight portions, more preferably 45 weight portions～65 weight portions.
A-1-2. ultra micron composition
In above-mentioned ultra micron composition, representative is can be used as the composition of adjusting substrate refractive index and plays a role.By using the ultra micron composition, can easily adjust the refractive index of matrix, thereby can enlarge the refringence of light diffusing particulate and matrix.Particularly according to the present invention, infiltrate into the light diffusing particulate by resinous principle inner, can improve the concentration of the ultra micron composition in matrix, therefore can easily enlarge the refringence of matrix and light diffusing particulate.Its result is, can though obtain but to have for film the light diffusion element of high haze value (strong diffusivity).Ultra micron composition preferred index n BSatisfy following formula (2):
0＜|n P-n A|＜|n P-n B|···(2)。
In formula (2), n AAnd n PFor as mentioned above.| n P-n B| be preferably 0.10～1.50, more preferably 0.20～0.80.If | n P-n B| do not reach 0.10, under most situations, mist degree is below 90%, and its result is that existence can't fully be spread when being loaded to liquid crystal indicator from the light of light source and might be made the visual angle narrow down.If | n P-n B| surpass 1.50, the possibility that exists backscattering to increase.
The ultra micron composition preferably contains with above-mentioned resinous principle and light diffusing particulate and is the compound of homology not, more preferably contains mineral compound.As preferred mineral compound, can enumerate for example 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 to Optical Absorption, and have the refractive index that is difficult to embody in the organic compounds such as ionization ray solidified resin or thermoplastic resin, therefore can enlarge the refringence of light diffusing particulate and matrix.And, these metal oxides and metal fluoride because of with resinous principle dispersed suitably, therefore can form at the near interface (periphery of light diffusing particulate) of light diffusing particulate and matrix other concentration adjustment district.Such other concentration adjustment district also is formed at the outside of light diffusion particulate, compares when the inner situation that forms the concentration adjustment district of light diffusing particulate thus with only, can further suppress backscattering.Mineral compound is particularly preferably zirconia.Its reason is, due to larger with the refringence of light diffusing particulate, and suitably dispersed with resinous principle, thereby can form well other concentration adjustment district with desired characteristic (or structure).Moreover, in the present invention, as long as in the inner concentration adjustment district of forming of the near surface of light diffusing particulate, also can not form above-mentioned other concentration adjustment district.
The refractive index of above-mentioned ultra micron composition is preferably below 1.40 or more than 1.60, more 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 do not reach 1.60, might cause the refringence of light diffusing particulate and matrix insufficient, when the light diffusion element that will obtain is used for the liquid crystal indicator of collimated back front diffusion system, can't fully spreads from the light of collimated back and cause the visual angle to narrow down.
Above-mentioned ultra micron composition also can reduce refractive index by porous materialization.
The mean grain size of above-mentioned ultra micron composition is preferably 1nm～100nm, 10nm～80nm more preferably, and then 20nm～70nm more preferably.So, by using mean grain size less than the ultra micron composition of light wavelength, can obtain not produce geometrical optics reflection, refraction, scattering and matrix uniformly on optics between ultra micron composition and resinous principle.Its result is to obtain uniform light diffusion element on optics.
Above-mentioned ultra micron composition is preferably the favorable dispersibility with above-mentioned resinous principle.In this manual, so-called " favorable dispersibility ", refer to coating with the coating liquid of above-mentioned resinous principle, ultra micron composition, (as required and a small amount of UV initiating agent) and solvent flashing mixing gained, and with solvent in addition dry removal the and film as transparent of acquisition.
Above-mentioned ultra micron composition has preferably carried out surface modification.By carrying out surface modification, the ultra micron composition is scattered in resinous principle well, and can forms well above-mentioned other concentration adjustment district.As surface modifying method, as long as can obtain effect of the present invention, just can adopt the method for any appropriate.Representative is that surface modification is to form the surface modifier layer by coating surface modifier on the surface of ultra micron composition to carry 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, can improve the wetting state of resinous principle and ultra micron composition, make the interface stability of resinous principle and ultra micron composition, the ultra micron composition is scattered in resinous principle well, and form well above-mentioned other concentration adjustment district.
With respect to formed matrix 100 weight portions, the allotment amount of the ultra micron composition in above-mentioned coating liquid is preferably 10 weight portions～70 weight portions, more preferably 35 weight portions～55 weight portions.
A-1-3. light diffusing particulate
As long as above-mentioned light diffusing particulate can form above-mentioned concentration adjustment district well, just can contain suitable material arbitrarily.The refractive index of above-mentioned light diffusing particulate preferably satisfies the relation of above-mentioned formula (1).As mentioned above, preferably to contain the resinous principle with above-mentioned matrix be the compound of homology to the light diffusing particulate.For example, when the ionization ray solidified resin of the resinous principle that consists of matrix was the situation of acrylic ester resin, the light diffusing particulate was also to contain the acrylic ester resin as preferred.More specifically, when the monomer component of the acrylic ester resin of the resinous principle that consists of matrix be for example the situation of above-mentioned PETA, NPGDA, DPHA, DPPA and/or TMPTA, the acrylic ester resin of formation light diffusing particulate was preferably polymethylmethacrylate (PMMA), polymethyl acrylate (PMA) and their multipolymer and their cross-linking agent.As with the copolymerization composition of PMMA and PMA, can enumerate polyurethane, polystyrene (PSt), melamine resin.The light diffusing particulate is particularly preferably and contains PMMA.Its reason is, and is suitable with the relation of the refractive index of the resinous principle of matrix or thermodynamic behaviour.In addition, the light diffusing particulate preferably has cross-linked structure (tridimensional network).Light diffusing particulate swellable with cross-linked structure.Therefore, such light diffusing particulate is different from fine and close or solid inorganic particulate, can make the precursor of the resinous principle with suitable intermiscibility infiltrate into well its inside.The cross-linking density of light diffusing particulate is preferably little (sparse) to the degree that can obtain desired penetration range (following).Light diffusing particulate when for example, being coated with above-mentioned coating liquid is preferably 110%～200% with respect to the swellbility of resinous principle precursor (also can contain solvent).Here, the ratio of the mean grain size of so-called " swellbility ", the mean grain size of particle that the refers to solvent swelling state particle before with respect to swelling.
The mean grain size of above-mentioned light diffusing particulate is preferably 1 μ m～5 μ m, and 1.5 μ m～4.0 μ m more preferably, and then 2.0 μ m～3.0 μ m more preferably are particularly preferably 2.1 μ m～2.4 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 element.So long as have the mean grain size of such ratio with respect to the thickness of light diffusion element, just can arrange a plurality of light diffusing particulates on the thickness direction of light diffusion element, therefore can be during incident light sees through light diffusion element, make this light MULTIPLE DIFFUSION, its result is for can obtain sufficient light diffusing.
The standard deviation that the weight average particle diameter of light diffusing particulate distributes is preferably below 1.0 μ m, more preferably below 0.5 μ m.Exist a plurality of particle diameters less than the light diffusing particulate of weight average particle diameter if mix, exist diffusivity too increase and can't suppress well backscattered situation.If mixing exists a plurality of particle diameters greater than the light diffusing particulate of weight average particle diameter, have the situation can't arrange a plurality of light diffusing particulates on the thickness direction of light diffusion element and can't obtain MULTIPLE DIFFUSION, its result is for existing 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 spherical shape, flakey, tabular, oval spherical, unsetting.When most situation, can use the spherical shape particulate as above-mentioned light diffusing particulate.
The refractive index of above-mentioned light diffusing particulate is preferably 1.30～1.70, and more preferably 1.40～1.60.
With respect to formed matrix 100 weight portions, the allotment amount of the light diffusing particulate in above-mentioned coating liquid is preferably 10 weight portions～100 weight portions, more preferably 15 weight portions～40 weight portions.The light diffusing particulate of the mean grain size with above-mentioned preferable range by for example containing such allotment amount can obtain to have the light diffusion element of very excellent light diffusing.
A-1-4. the integral body of coating liquid consists of
As above-mentioned volatile solvent, as long as can make above-mentioned each composition dissolving or Uniform Dispersion, just 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 coating liquid can be according to purpose, and then contains suitable adjuvant arbitrarily.When for example stating in the use the situation of ultra micron composition, disperse well in order to make the ultra micron composition, can suitably use spreading agent.As other concrete example of adjuvant, can enumerate antiaging agent, modifier, surfactant, anti-blushing agent, ultraviolet light absorber, levelling agent, defoamer.
The solid component concentration of above-mentioned coating liquid can be adjusted to be become about preferred 10 % by weight～70 % by weight.As long as for such solid component concentration, just can obtain to have the coating liquid of the viscosity of easy coating.
A-2. process B
Infiltrate into the method for the inside of above-mentioned light diffusing particulate as at least a portion that makes above-mentioned precursor in process B, representatively enumerate the method that above-mentioned coating liquid is standing.Resinous principle and light diffusing particulate preferably contain the material of homology, more preferably contain the high material of intermiscibility, therefore by coating liquid is standing, even do not carry out special processing or operation, the precursor of resinous principle (monomer) also can infiltrate into the inside of light diffusing particulate.That is, contact the stipulated time by the precursor that makes resinous principle with the light diffusing particulate, the front cognition of resinous principle infiltrates into the inside of light diffusing particulate.Time of repose is preferably the longer time of time till particle diameter than light diffusing particulate reaches in fact maximum.Here, so-called " particle diameter of light diffusing particulate reaches in fact the time till maximum ", refer to until the light diffusing particulate is swelling to time till swelling (that is, becoming equilibrium state) to greatest extent and further (below, also referred to as the maximum swelling time).The time that precursor by making resinous principle and light diffusing particulate contact gear ratio maximum swelling time are longer, the resinous principle precursor is to the infiltration of the light diffusing particulate state that can reach capacity, and can't further enter to the cross-linked structure of light diffusing particulate inside.Its result is, by following polymerization process, and can be well and stably in the inner concentration adjustment district of forming of the near surface of light diffusing particulate.The maximum swelling time can change according to the intermiscibility of resinous principle and light diffusing particulate.Therefore, time of repose can change according to the constituent material of resinous principle and light diffusing particulate.For example, time of repose is preferably 1 hour～and 48 hours, more preferably 2 hours～40 hours, and then more preferably 3 hours～35 hours, be particularly preferably 4 hours～30 hours.If time of repose does not reach 1 hour, exist precursor not infiltrate into fully the situation of light diffusing particulate inside, its result is to exist and can not form well the situation in concentration adjustment district.If time of repose surpasses 48 hours, might be because the physical property between the light diffusing particulate interact, and cause the light diffusing particle coagulation, and the viscosity of coating liquid raises, and it is insufficient that screening characteristics becomes.Standing can at room temperature carrying out also can carry out under according to purpose or the set point of temperature condition of using material to set.
In process B, above-mentioned precursor is as long as infiltrate into the part of this light diffusing particulate from the surface of above-mentioned light diffusing particulate, till for example preferably infiltrating into 10%～95% the scope of mean grain size of above-mentioned light diffusing particulate.When penetration range did not reach 10% situation, existence can not form well the concentration adjustment district and can't fully reduce backscattered situation.Even penetration range surpasses 95%, same during also with the less situation of penetration range, exist can not form well the concentration adjustment district and can't fully reduce backscattered situation.The material that penetration range can be by adjusting resinous principle and light diffusing particulate, the cross-linking density of light diffusing particulate, time of repose, dwell temperature etc. and controlled.
In the present invention, importantly control above-mentioned precursor to the infiltration of light diffusing particulate.For example, as shown in Figure 3, this coating liquid is coated after the above-mentioned coating liquid of preparation on base material and when forming the situation of light diffusion element, the diffusion half-power angle can significantly change according to baking temperature at once.On the other hand, standing for example coat after 24 hours on base material and when forming the situation of light diffusion element, the diffusion half-power angle can not be subjected to effect of drying temperature and be roughly fixing with above-mentioned coating liquid.Can think that its reason is, by standing, front cognition infiltrates into state of saturation to the light diffusing particulate, so the formation in concentration adjustment district is not subjected to effect of drying temperature.Therefore, as mentioned above, time of repose is preferably the time longer than the maximum swelling time.By setting time of repose like this, can obtain not to be subjected to the impact of drying time and fixing and good diffusion half-power angle roughly, but therefore stably make to bias free the high light diffusion element of diffusivity.In addition, for example can make by the low temperature drying of 60 ℃, therefore also preferred from security or cost aspect.On the other hand, as long as can determine according to the kind of precursor and light diffusing particulate until infiltration reaches capacity the time till state, just can suitably select baking temperature, thus, even the shortening time of repose, but also stably make to bias free the high light diffusion element of diffusivity.For example, when forming the situation of light diffusion element even this coating liquid is coated on base material after the above-mentioned coating liquid of preparation at once, also can be by baking temperature being set as 100 ℃, make precursor infiltration inner and form the concentration adjustment district to the light diffusing particulate, thereby bias free ground is stablized and is made the high light diffusion element of diffusivity.
A-3. operation C
Representative is at operation C (making the operation of precursor generation polymerization) before, above-mentioned coating liquid to be coated base material.As base material, as long as can obtain effect of the present invention, just 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 also can carry out the surface modifications such as easy bonding processing as required, and also can contain the adjuvants such as lubricant, antistatic agent, ultraviolet light absorber.There is the situation that can be used as protective seam and play a role in this base material in following polarization plates with light diffusion element.
As the coating process to the above-mentioned coating liquid of base material coating, can adopt the method for having used any suitable coating machine.As the concrete example of coating machine, can enumerate rod coater, oppositely coating machine, soft-touch type coating machine, intaglio printing coating machine, mould are coated with machine, point type coating machine.
Secondly, make above-mentioned precursor generation polymerization.Polymerization can adopt according to the kind of resinous principle (thereby its precursor) suitable method arbitrarily.For example, when resinous principle is the situation of ionization ray solidified resin, make precursor generation polymerization by irradiation ionization property ray.When using the situation of ultraviolet ray conduct ionization property ray, its accumulative total light quantity is preferably 200mJ～400mJ.Ionization property ray is preferably more than 70% with respect to the transmissivity of light diffusing particulate, more preferably more than 80%.In addition, for example when resinous principle is the situation of thermohardening type resin, make precursor generation polymerization by heating.Heating-up temperature and heat time heating time can suitably be set according to the kind of resinous principle.Polymerization is preferably undertaken by irradiation ionization property ray.So long as ionization property radiation exposure just can make curing of coating under the state that keeps well refractive index distribution structure (concentration adjustment district), therefore can make the good light diffusion element of diffusion property.By making precursor generation polymerization, and form matrix, and simultaneously in the inner concentration adjustment district of forming of the near surface of light diffusing particulate.More specifically, the concentration adjustment district is that the precursor of the inside by infiltrating into the light diffusing particulate carries out polymerization and forms; Matrix is to carry out polymerization by the precursor that does not infiltrate into the light diffusing particulate to form.Namely, manufacture method according to present embodiment, polymerization occurs simultaneously by the precursor that makes the precursor that infiltrates into light diffusing particulate inside and do not infiltrate into the light diffusing particulate, can be in the inner concentration adjustment district of forming of the near surface of light diffusing particulate, and form simultaneously matrix.In one embodiment, can and then be formed with other concentration adjustment district at the near interface (periphery of light diffusing particulate) of light diffusing particulate and matrix.Other concentration adjustment district is mainly that the intermiscibility because of resinous principle, ultra micron composition and light diffusing particulate forms.
The manufacture method of light diffusion element of the present invention except containing above-mentioned operation A～operation C, also can contain suitable operation, processing and/or operation arbitrarily at any reasonable time point certainly.The kind of such operation etc. and the time point that carries out such operation etc. can suitably be set according to purpose.For example, the manufacture method of light diffusion element of the present invention can be as required and then contain the coating liquid dry operation in addition that will coat on base material.Such drying for example can be carried out before polymerization process, also can carry out after polymerization process.
As the drying means of above-mentioned coating liquid, can adopt suitable method arbitrarily.As concrete example, can enumerate natural drying, heat drying, drying under reduced pressure.Take heat drying as preferred.Heating-up temperature is for example 60 ℃～150 ℃, and be for example 30 seconds～5 minutes heat time heating time.
Form in the above described manner light diffusion element on base material.The light diffusion element that obtains can be peeled off and as solid memder from base material, also can be used as the light diffusion element with base material, also can be needed on polarization plates etc. and as composite component the polarization plates of light diffusion element (for example with) from base material, also can be together with base material be attached at polarization plates etc. as composite component the polarization plates of light diffusion element (for example with).During as the situation of the composite component polarization plates of light diffusion element (for example with), this base material can be used as the protective seam of polarization plates and plays a role be attached at polarization plates etc. together with base material.
B. light diffusion element
Light diffusion element of the present invention can obtain by the above-mentioned method that the A-1 item～the A-3 item is put down in writing.Light diffusion element of the present invention has the matrix that contains resinous principle and ultra micron composition and is scattered in light diffusing particulate in this matrix.Light diffusion element of the present invention is that the refringence by matrix and light diffusing particulate embodies light diffusion function.Fig. 1 is the mode chart of the disperse state of the resinous principle of matrix of the light diffusion element that obtains for the manufacture method of explanation by the preferred embodiment of the present invention and light diffusing particulate.Light diffusion element 100 of the present invention has the matrix 10 that contains resinous principle 11 and ultra micron composition 12 and is scattered in light diffusing particulate 20 in matrix 10.The refractive index of the resinous principle of matrix and light diffusing particulate preferably satisfies following formula (1):
0＜|n P-n A|···(1)。
The refractive index of above-mentioned ultra micron composition satisfies following formula (2):
0＜|n P-n A|＜|n P-n B|···(2)。
The ultra micron composition that use has the resinous principle of matrix of relation of above-mentioned formula (1) and light diffusing particulate and uses the relation with above-mentioned formula (2) can obtain not only keeping higher mist degree but also suppress backscattered light diffusion element thus.
In light diffusion element of the present invention, be formed with concentration adjustment district 30 in the near surface inside of light diffusing particulate 20.As illustrated in above-mentioned A-1 item～A-3 item, concentration adjustment district 30 is that the precursor (monomer) by resinous principle 11 infiltrates into light diffusing particulate 20 and polymerizations occurs after inner and form.In one embodiment, in concentration adjustment district 30, the weight concentration of resinous principle 11 is essentially fixing.In another embodiment, in concentration adjustment district 30, the weight concentration of resinous principle 11 is along with reducing away from (that is, along with the center towards light diffusing particulate 20) from the surface of light diffusing particulate 20.Concentration adjustment district 30 is preferably formed in the inside of light diffusing particulate 20, as long as so just can bring into play its effect.For example, the concentration adjustment district is formed on from the surface of light diffusing particulate 20 10%～95% scope to the mean grain size of this light diffusing particulate.The thickness in concentration adjustment district 30 (distance from the light diffusing microparticle surfaces till the concentration adjustment district penetralia) both can be fixing, also can be according to the position of light diffusing microparticle surfaces and difference.The thickness in concentration adjustment district 30 is preferably 100nm～4 μ m, more preferably 100nm～2 μ m.Resinous principle 11 forms concentration adjustment district 30 through infiltration, can obtain following effect thus: (1) can spread at light the near interface of particulate and matrix, make the interim ground of refractive index or in fact continuity ground change (with reference to Fig. 2 (a)).On the other hand, in light diffusion element formerly, do not form such concentration adjustment district, the interface of particulate and matrix is obvious, so refractive index is discontinuously to the variations in refractive index (with reference to Fig. 2 (b)) of matrix from the refractive index of particulate.As shown in Fig. 2 (a), form concentration adjustment district 30 and make in matrix 10 with the interim ground of the near interface refractive index of light diffusing particulate 20 or in fact continuity change, even increase thus the refringence of matrix 10 and light diffusing element 20, also can suppress the reflection at the interface of matrix and light diffusing particulate, thereby can suppress backscattering.On the other hand, as shown in Fig. 2 (b), according to previous light diffusion element, when wish is given strong diffusivity (high haze value) by enlarging refringence, can't eliminate the gap of the refractive index on the interface.Its result is, because the backscattering due to boundary reflection becomes large; (2) when mainly forming the situation in other concentration adjustment district because of the ultra micron composition, can promote its formation; (3) infiltrate into light diffusing particulate 20 inside by resinous principle 11, and compare during with the situation of not infiltration, the concentration of the resinous principle 11 in matrix 10 reduces.Its result is, the refractive index of ultra micron composition 12 becomes large to the help of the refractive index of matrix integral body, therefore when the larger situation of the refractive index of ultra micron composition, the refractive index increase of matrix integral body (otherwise, when the less situation of the refractive index of ultra micron composition, the refractive index of matrix integral body diminishes), the refringence of matrix and light diffusing particulate further increases.Therefore, compare during with situation that resinous principle does not permeate, can realize higher diffusivity (haze value).
As illustrated in above-mentioned A-1 item～A-3 item, above-mentioned concentration adjustment district be can be by suitably selecting matrix resinous principle and the constituent material of light diffusing particulate and chemistry and thermodynamic behaviour form.For example, by consisting of resinous principle and light diffusing particulate with intermiscibility in based material higher material gang, can form well thus the concentration adjustment district.The resinous principle that the thickness in concentration adjustment district and concentration gradient can be by adjusting matrix and the chemistry of light diffusing particulate and thermodynamic behaviour and controlled.
Suitably select above-mentioned ultra micron composition according to the kind of above-mentioned resinous principle and above-mentioned light diffusing particulate, can and then form other concentration adjustment district (not shown) at the near interface (periphery of light diffusing particulate) of matrix 10 and light diffusing particulate 20 thus.For example, consist of resinous principle and light diffusing particulate by the material of homology (for example organic compound gang), and material (for example mineral compound) consists of the ultra micron composition by being not homology with matrix and light diffusing particulate, can form well thus other concentration adjustment district.More specifically, about above-mentioned resinous principle, compare with near the state that dissolves with the ultra micron homogeneous chemical composition light diffusing particulate locally or disperse, only surround the light diffusing particulate by resinous principle, can make the energy stabilization of whole system.Its result is, the weight concentration of resinous principle in the zone near the light diffusing particulate, higher than the average weight concentration of the resinous principle in matrix integral body, and along with from the light diffusing particulate away from and reduce.Therefore, can form other concentration adjustment district.
In above-mentioned other concentration adjustment district, along with from light diffusing particulate 20 away from, the weight concentration of resinous principle 11 reduces, and the weight concentration of ultra micron composition uprises.In other words, in the zone near light diffusing particulate 20 in other concentration adjustment district, the ultra micron composition is to disperse with relatively low concentration, and the concentration of ultra micron composition along with from light diffusing particulate 20 away from and increase.For example, in the zone near light diffusing particulate 20 in other concentration adjustment district, the weight concentration of resinous principle is higher than the average weight concentration of the resinous principle in matrix integral body, and the weight concentration of ultra micron composition is lower than the average weight concentration of the ultra micron composition in matrix integral body.On the other hand, in other concentration adjustment district in light diffusing particulate 20 is counted farthest zone, the weight concentration of resinous principle equals or sometimes lower than the average weight concentration of the resinous principle in matrix integral body, and the weight concentration of ultra micron composition equals or sometimes higher than the average weight concentration of the ultra micron composition in matrix integral body.By such other concentration adjustment district also being formed at the outside of light diffusion particulate, can increase that above-mentioned refractive index is interim ground or the zone that changes, continuity ground is (namely in fact, can be till other concentration adjustment district in the concentration adjustment district of light diffusing particulate inboard to the light diffusing particulate outside, make the interim ground of refractive index or in fact continuity ground change).Its result is, and only compares when the inner situation that forms the concentration adjustment district of light diffusing particulate, can further suppress backscattering.In addition, the outside in other concentration adjustment district, the weight concentration that the refractive index of refractive index and light diffusing particulate 20 differs larger ultra micron composition relatively uprises, and therefore can enlarge the refringence of matrix 10 and light diffusing particulate 20.Its result is even be film, also can realize higher mist degree (strong diffusivity).Such feature is specially adapted to require the purposes of strong diffusivity (mist degree is more than 90%) as the light diffusion element that uses in the diffusion system of collimated back front.
The thickness in above-mentioned other concentration adjustment district (distance from the light diffusing microparticle surfaces till other concentration adjustment district end) both can be fixing (namely, other concentration adjustment district also can be concentric spherical expansion around the light diffusing particulate), also can make according to the position of light diffusing microparticle surfaces thickness different (for example also can become the outer contoured shape as candy).The thickness in other concentration adjustment district is preferably according to the position of light diffusing microparticle surfaces and difference.As long as be such formation, refractive index is more changed on continuity ground.As long as form other concentration adjustment district with sufficient thickness, refractive index is changed on continuity ground more smoothly, thereby can very effectively suppress backscattering.On the other hand, if thickness is excessive, exists other concentration adjustment district even to take the zone that original light diffusing particulate should exist, and can't obtain the situation of sufficient light diffusing (for example haze value).Therefore, the thickness in other concentration adjustment district is preferably 10nm～500nm, 20nm～400nm more preferably, and then 30nm～300nm more preferably.In addition, the thickness in other concentration adjustment district is preferably 10%～50% with respect to the mean grain size of light diffusing particulate, and more preferably 20%～40%.
The mist degree of above-mentioned light diffusion element is more high better, particularly, is preferably 90～99%, and more preferably 92～99%, and then more preferably 95～99%, be particularly preferably 97～99%.Be more than 90% by mist degree, can be preferably as the front light diffusion element of collimated back front diffusion system.Moreover, so-called collimated back front diffusion system, refer to use collimated back light (to fixed-direction optically focused and the wide narrower light backlight of brightness full width at half maximum) in liquid crystal indicator, and be provided with the system of front light diffusion element in the identification side of upside polarization plates.
The diffusion property of above-mentioned light diffusion element, if represent with light diffusion half-power angle, be preferably 10 °～150 ° (one-sided 5 °～75 °), more preferably 10 °～100 ° (one-sided 5 °～50 °), and then more preferably 30 °～80 ° (one-sided 15 °～40 °).
The thickness of above-mentioned light diffusion element can suitably be set according to purpose or desired diffusion property.Particularly, the thickness of above-mentioned light diffusion element is preferably 4 μ m～50 μ m, more preferably 4 μ m～20 μ m.According to the present invention, although be very thin thickness like this, also can obtain to have the light diffusion element of very high as mentioned above mist degree.
Above-mentioned light diffusion element is suitable for the backlight of identification side member, liquid crystal indicator of liquid crystal indicator and uses pervasion component with member, ligthing paraphernalia (for example organic EL, LED), especially is suitable as the front diffused component of collimated back front diffusion system.Above-mentioned light diffusion element both can be provided as membranaceous or tabular component separately, also can be attached at arbitrarily suitable base material, polarization plates and was provided as composite component.In addition, also can be on light diffusion element stacked anti-reflecting layer.
C. with the polarization plates of light diffusion element
C-1. the integral body with the polarization plates of light diffusion element consists of
The manufacture method of the polarization plates with light diffusion element of the present invention is used the manufacture method of the light diffusion element of the present invention of putting down in writing in above-mentioned A-1 item～A-3 item and carries out.By the polarization plates with light diffusion element that manufacture method of the present invention obtains, representative is the identification side that is disposed at liquid crystal indicator.Fig. 4 is the summary section with the polarization plates of light diffusion element of the preferred embodiment of the present invention.This polarization plates 200 with light diffusion element has light diffusion element 100 and polaroid 110.Light diffusion element 100 is fastened and is stated the light diffusion element of the present invention of putting down in writing in A-1 item～A-3 item and B item.Light diffusion element 100 is configured to become when the polarization plates with light diffusion element is disposed at the situation of identification side of liquid crystal indicator by the identification side.In one embodiment, the identification side at light diffusion element 100 disposes low reflection layer or anti-reflex treated layer (antireflection processing layer) (not shown).In illustrated example, be to have protective seam 120 and 130 in the both sides of polaroid with the polarization plates 200 of light diffusion element.Light diffusion element, polaroid and protective seam are to attach via arbitrarily suitable adhesive layer or adhesive phase.At least one in protective seam 120 and 130 also can omit according to the formation of purpose, polarization plates and the formation of liquid crystal indicator.For example, the base material that uses when forming light diffusion element can be used as protective seam and during the situation that plays a role, can omit protective seam 120.Polarization plates with light diffusion element of the present invention especially can be suitable as the identification lateral deviation vibration plate in the liquid crystal indicator that adopts collimated back front diffusion system.
C-2. polaroid
As above-mentioned polaroid 110, can adopt suitable polaroid arbitrarily according to purpose.Such as enumerating: make the dichroic substance such as iodine, dichroic dye be adsorbed in polyvinyl alcohol mesentery, part formalizing polyvinyl alcohol mesentery, vinyl-vinyl acetate copolymer pastern and divide the hydrophilic macromolecule film such as saponification film and the film that forms of uniaxial extension in addition; The polyenoid such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA), Polyvinylchloride are alignment films etc.Wherein, make the dichroic substance such as iodine be adsorbed in polyvinyl alcohol mesentery and the polaroid that forms of uniaxial extension in addition, the polarisation dichroic ratio is high, therefore particularly preferably.Thickness for these polaroids is not particularly limited, and is generally about 1～80 μ m.
Make iodine be adsorbed in polyvinyl alcohol mesentery and the polaroid that forms of uniaxial extension in addition, for example can be by dyeing in the aqueous solution that polyvinyl alcohol film be impregnated in iodine, and extend to 3～7 times of former length and make.Also can contain as required boric acid, zinc sulfate, zinc chloride etc., also can impregnated in the aqueous solution of potassium iodide etc.In addition, also can wash in before dyeing, polyvinyl alcohol mesentery being impregnated in water as required.
By polyvinyl alcohol mesentery is washed, dirt, the antiblocking agent that falls the polyvinyl alcohol mesentery surface capable of washing not only, and have because the polyvinyl alcohol mesentery swelling being prevented from dye unequal inhomogeneous effect.Extension can utilize iodine to carry out after dyeing, on one side also can extend by an Edge Coloring, in addition, also can utilize immediately iodine to dye after extending.Also can be in the aqueous solution of boric acid, potassium iodide etc., extend in water-bath.
C-3. protective seam
Above-mentioned protective seam 120 and 130 is formed at any suitable film by the protective seam that can be used as polarization plates.As the concrete example of the material of the major component that becomes this film, can enumerate the cellulose-based resins such as triacetyl cellulose (TAC); Or the transparent resin such as polyester system, polyethenol series, polycarbonate-based, polyamide-based, polyimide system, polyethersulfone system, polysulfones system, polystyrene, norborene system, polyolefin, (methyl) acrylic acid series, acetic acid esters system etc.In addition, also can enumerate the thermohardening type resin such as (methyl) acrylic acid series, carbamate system, (methyl) propenoic methyl carbamate system, epoxy system, silicone-based or ultraviolet curing resin etc.In addition, also can enumerate such as vitreous based polymers such as siloxane-based polymers.In addition, also can use the polymer film of putting down in writing in Japanese Patent Laid-Open 2001-343529 communique (WO01/37007).Material as this film, can use the resin combination that for example contains the thermoplastic resin that has the phenyl that is substituted or is unsubstituted and itrile group on the thermoplastic resin that has the imide that is substituted or is unsubstituted on side chain and side chain, for example, can enumerate to have and contain isobutylene and the alternating copolymer of N-methyl maleimide and the resin combination of acrylonitritrile-styrene resin.This polymer film can be for example extrusion molding thing of above-mentioned resin combination.
Above-mentioned protective seam (inboard protective seam) 130 preferably optically has isotropy.Particularly, the phase differential Rth (550) of the thickness direction of inboard protective seam is preferably-20nm～+ 20nm, more preferably-10nm～+ 10nm, be particularly preferably-6nm～+ 6nm, the best is-3nm～+ 3nm.In the face of inboard protective seam, phase differential Re (550) is preferably below the above 10nm of 0nm, more preferably below the above 6nm of 0nm, is particularly preferably below the above 3nm of 0nm.About forming the concrete condition that has the film of isotropic protective seam on such optics, be recorded in Japanese Patent Laid-Open 2008-180961 communique, this record is incorporated in this instructions as a reference.
D. liquid crystal indicator
The manufacture method of liquid crystal indicator of the present invention is to use the manufacture method of the light diffusion element of the present invention of putting down in writing in above-mentioned A-1 item～A-3 item and carry out.Fig. 5 is the summary section of the liquid crystal indicator that obtains of the manufacture method by the preferred embodiment of the present invention.Liquid crystal indicator 500 has: liquid crystal cells 510, in the polarization plates 520 and 530 of liquid crystal cells both sides configuration; Backlight assembly 540 in polarization plates 530 arranged outside; And the light diffusion element 100 that arranges in polarization plates 520 outsides (identification side).Can according to purpose, any suitable optical compensation plate (polarizer) be disposed between liquid crystal cells 510 and polarization plates 520 and/or 530.Liquid crystal cells 510 has a pair of substrate (representative is glass substrate) 511 and 512 and be disposed at the liquid crystal layer 513 as the liquid crystal of display medium of containing between substrate 511 and 512.
Light diffusion element 100 is light diffusion elements of the present invention of putting down in writing in above-mentioned A-1 item～A-3 item and B item.Perhaps, the polarization plates with light diffusion element of the present invention of also putting down in writing in configurable above-mentioned C item replaces light diffusion element 100 and identification lateral deviation vibration plate 520.Light diffusion element is light (representative is collimated light as described below) transmission and the diffusion that makes through liquid crystal cells.
Above-mentioned backlight assembly 540 is to penetrate the parallel light source device of collimated light towards liquid crystal cells 510.Backlight assembly can have any suitable formation that can penetrate collimated light.For example, the backlight assembly collective optics (all not shown) that has light source and the light that penetrates from light source is collimated and processes.When this situation, as collective optics, can adopt any suitable collective optics that can collimate to the light that penetrates from light source and process.When light source itself can penetrate the situation of collimated light, can omit collective optics.As the concrete formation of backlight assembly (parallel light source device), can enumerate for example formation of the following stated: the collective optics that (1) will be provided with in the part except lens focus of the tabular surface side of biconvex lens (Lenticular Lens) or bullet cut lens light shield layer or reflection horizon is disposed at the formation (for example Japanese Patent Laid-Open 2008-262012 communique) of the liquid crystal cell side of light source (for example cold-cathode fluorescence lamp); (2) have side light type LED light source, its light guide plate and (in this formation, can as required and then use the anisotropy diffused component in the formation of angle prism that the light guide plate side is formed with convex surface and is disposed at the liquid crystal cell side of this light guide plate; For example No. the 3442247th, Jap.P.); (3) light shield layer that light absorption resin and transparent resin is alternately formed striated is disposed at the formation (for example, Japanese Patent Laid-Open 2007-279424 communique) between backlight and backlight side polarization plates; (4) use bullet cut LED as the formation (for example, Japanese patent laid-open 6-130255 communique) of light source; (5) use the formation (for example, Japanese patent laid-open 1-126627 communique) of the diffuser plate that has Fresnel lens to reach as required and use.The above-mentioned communique that records their detailed formation is to be incorporated in this instructions as a reference.
It is vertical orientated liquid crystal molecule when liquid crystal layer 513 preferably contains black display.drive pattern as the liquid crystal cells with such liquid crystal layer, can enumerate for example MVA (Multi-domain Vertical Alignment, wide area is vertical orientated) pattern, PVA (pattern VA (Pattern Vertical Alignment, pattern is vertical orientated)) pattern, TN (twisted nematic (Twisted Nematic)) pattern, ECB (electrically conerolled birefringence (Electrically Controlled Birefringence)) pattern, OCB (Optically Compensated Bend, optical compensation curved) (crooked to row (bend nematic)) pattern.
Embodiment
Below, illustrate the present invention by embodiment, but the present invention is not limited to these embodiment.Evaluation method in embodiment is as described below.In addition, as long as not dated especially, " part " in embodiment to reach " % " be weight basis.
(1) thickness of light diffusion element
Utilize micrometering formula thickness gauge (manufacturing of three rich (Mitutoyo) company) to measure the aggregate thickness of base material and light diffusion element, and deduct the thickness of base material and calculate the thickness of light diffusion element from this aggregate thickness.
(2) the concentration adjustment district has or not
To the light diffusion element that obtains in embodiment and comparative example and the duplexer of base material, it is cooling that one side uses liquid nitrogen to carry out, and one side utilizes microtome to be sliced into the thickness of 0.1 μ m, and as working sample.Use transmission electron microscope (TEM), observe the state of the light diffusion element particulate partly of this working sample.To can confirm that in particulate inside situation by the caused contrast of precursor infiltration is made as " have concentration adjustment district ", and will can't confirm contrast in particulate inside and be that the situation of even look is made as " without the concentration adjustment district ".
(3) mist degree
According to the method for defined in JIS 7136, use haze meter (in the village, company of color Science Institute makes, trade name " HN-150 ") to measure mist degree.
(4) light diffusion half-power angle
Front illuminated laser light from light diffusion element, and utilize goniophotometer (goniophotometer) every 1 ° ground measuring the diffusion brightness with respect to the diffusion angle of the light spread, as shown in Figure 6, become the diffusion angle of a half intensity in the light self-diffusion brightness maximal value of the both sides of diffusion mensuration except the transmitted light that advances of laser, the value (angle A+angle A of Fig. 6 ') that adds the angle of these both sides and obtain is spread half-power angle as light.
(5) backscattering ratio
The light diffusion element that obtains in embodiment and comparative example and the duplexer of base material are fitted in (the sumitomo chemical company manufacturing of black acrylic panel via clear binder, trade name " SUMIPEX " (registered trademark), thickness is 2mm) on, and as working sample.Utilize spectrophotometer (tester company of Hitachi makes, trade name " U4100 ") to measure the integrated reflectivity of this working sample.On the other hand, use from above-mentioned light diffusion element and remove with coating liquid the coating liquid that particulate forms, make the duplexer of base material and transparent overlay, and sample in contrast, with the above-mentioned the same integrated reflectivity (being surface reflectivity) of having measured.Deduct the integrated reflectivity (surface reflectivity) of above-mentioned control sample from the integrated reflectivity of said determination sample, calculate thus the backscattering ratio of light diffusion element.
(6) penetration range of precursor
From selecting 10 light diffusing particulates so that the TEM photo of the sequential shoot put down in writing above-mentioned (2) is random.For each of selected light diffusing particulate, measuring the particle diameter of light diffusing particulate and the not infiltration of light diffusing particulate has the particle diameter of the part (non-permeate portion) of precursor, and calculates penetration range according to following formula.The mean value of 10 light diffusing particulates is made as penetration range.
(penetration range)={ 1-(particle diameter of the particle diameter of non-permeate portion/light diffusing particulate) } * 100 (%)
＜embodiment 1: the making of light diffusion element 〉
(mean grain size is 60nm at the zirconium oxide nano-particle as the ultra micron composition that contains 62%, refractive index is 2.19) be coated with firmly that (JSR company makes with resin, in 18.2 parts of trade names " Opstar KZ6661 " (containing MEK/MIBK), interpolation is as pentaerythritol triacrylate (Osaka organic chemistry industrial group manufacturing of the precursor of resinous principle, trade name " Viscoat#300 ", refractive index is 1.52) 6.8 parts of 50%MEK solution, (Ciba company makes Photoepolymerizationinitiater initiater, trade name " Irgacure 907 ") 0.068 part, (DIC company makes levelling agent, trade name " GRANDIC PC4100 ") 0.625 part, reach polymethylmethacrylate (PMMA) particulate (the industrial group's manufacturing on root as the light diffusing particulate, trade name " ARTPEARL J4P ", mean grain size is 2.1 μ m, refractive index is 1.49) 2.5 parts.This potpourri is carried out 5 minutes ultrasound waves process, the preparation Uniform Dispersion has the coating liquid of above-mentioned each composition.Use rod coater that this coating liquid is coated on TAC film (Fuji Photo Film Co., Ltd. makes, trade name " Fujitac "), and with 100 ℃ of dryings after 1 minute, irradiation accumulative total light quantity is the ultraviolet ray of 300mJ, is the light diffusion element of 15 μ m and obtain thickness.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).With the results are shown in table 1 of result and following embodiment 2～4.In addition, the TEM photo with the light diffusion element section is shown in Fig. 7.According to this TEM photo, confirm to be formed with in the inside of light diffusing particulate the concentration adjustment district.
＜embodiment 2: the making of light diffusion element 〉
Prepare coating liquid in the mode identical with embodiment 1.This coating liquid after standing 4 hours, is applied in the mode identical with embodiment 1.Baking temperature after coating is made as 60 ℃, and thickness is made as 10 μ m, in addition, obtain light diffusion element in the mode identical with embodiment 1.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).Show the result in table 1.
＜embodiment 3: the making of light diffusion element 〉
Be made as 60 ℃ with having applied the baking temperature after the coating liquid, in addition, obtain light diffusion element in the mode identical with embodiment 1.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).Show the result in table 1.In addition, the TEM photo with the light diffusion element section is shown in Fig. 7.According to this TEM photo, confirm to be formed with in the inside of light diffusing particulate the concentration adjustment district.
＜embodiment 4: the making of light diffusion element 〉
Use the PMMA particulate (always to grind chemical company and make, MX180TA) as the light diffusing particulate, and thickness is made as 20 μ m, in addition, obtain light diffusion element in the mode identical with embodiment 1.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).Show the result in table 1.In addition, the TEM photo with the light diffusion element section is shown in Fig. 7.According to this TEM photo, confirm to be formed with in the inside of light diffusing particulate the concentration adjustment district.
＜embodiment 5: the making of light diffusion element 〉
Prepare coating liquid in the mode identical with embodiment 1.After standing 2 hours of this coating liquid, obtain light diffusion element in the mode identical with embodiment 2.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).Show the result in table 1.
＜embodiment 6: the making of light diffusion element 〉
Prepare coating liquid in the mode identical with embodiment 1.After standing 7 hours of this coating liquid, obtain light diffusion element in the mode identical with embodiment 2.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).Show the result in table 1.
＜embodiment 7: the making of light diffusion element 〉
Prepare coating liquid in the mode identical with embodiment 1.After standing 24 hours of this coating liquid, obtain light diffusion element in the mode identical with embodiment 2.The light diffusion element that obtains is used for the evaluation of above-mentioned (1)～(6).Show the result in table 1.
[table 1]
Figure BDA0000092280540000221
＜embodiment 8: the making of liquid crystal indicator 〉
Take out liquid crystal cells from the commercially available LCD TV (Sony Corporation makes, BRAVIA20 type, trade name " KDL20J3000 ") of liquid crystal cells with wide area type VA pattern.In the both sides of this liquid crystal cells, the commercially available polarization plates so that the mode of the absorption axes quadrature of each polaroid is fitted (day eastern electrician company make, trade name " NPF-SEGl423DU ").More specifically, become vertical direction (with respect to the long side direction of liquid crystal panel as 90 °) take the absorption axes direction of the polaroid of backlight side polarization plates, and the mode that the absorption axes direction of the polaroid of identification lateral deviation vibration plate becomes horizontal direction (long side direction with respect to liquid crystal panel is 0 °) is fitted.And then, the light diffusion element of embodiment 1 from the base material transfer printing and fit in the outside of identification lateral deviation vibration plate, and has been made liquid crystal panel.
On the other hand, at the single face of PMMA sheet material, use transfer roll to carry out melt thermal transfer to the pattern of biconvex lens.With the face (even surface) of the face opposition side that is formed with lens pattern on so that the light pattern of the mode AM aluminum metallization of transmission lens focus only, the area ratio that forms peristome is the reflection horizon of 7% (area ratio of reflecting part is 93%).Make in such a manner collective optics.(Sony Corporation makes to use cold-cathode fluorescence lamp, the CCFL of BRAVIA20J (Cold Cathode Fluorescent Lamp, cold-cathode fluorescence lamp)) as light source backlight, on this light source, collective optics is installed, and is made the parallel light source device (backlight assembly) that penetrates collimated light.
The above-mentioned backlight assembly of packing in above-mentioned liquid crystal panel, and make the liquid crystal indicator of collimated back front diffusion system.Make the liquid crystal indicator that obtains in the dark carry out white displays and black display, and its show state of visualization.Its result is, demonstrates when oblique observation the higher good display characteristic of brightness of the black and white displays in the dark of the black display at bright place.
＜estimate
By the sequentially record of embodiment and table 1 as can be known, manufacture method according to light diffusion element of the present invention, need not to carry out special processing or operation (in fact, only by make this precursor generation polymerization after the precursor that has mixed light diffusing particulate and matrix resin composition), just can make the light diffusion element with concentration adjustment district.By such light diffusion element being used for the liquid crystal indicator of collimated back front diffusion system, can obtain to have the liquid crystal indicator of the black and good display characteristic that brightness white displays in the dark is higher of black display at bright place.In addition, embodiment 1～3 and 5～7 is compared as can be known, so long as till precursor reaches capacity state to the infiltration in the light diffusing particulate, time of repose is longer, higher diffusible light diffusion element will be obtained to have, if reached capacity state, even time of repose is elongated, the diffusivity of the light diffusion element that obtains is also for roughly fixing.In addition as can be known, form the concentration adjustment district by guaranteeing specific time of repose, even carry out drying with low temperature, also can obtain to have the light diffusion element (low temperature drying cost and security aspect during fabrication is excellent, therefore preferred) of higher haze value.
Utilizability on industry
The light diffusion element that obtains by manufacture method of the present invention and with the polarization plates of light diffusion element, the backlight of identification side member, liquid crystal indicator that is suitable for liquid crystal indicator used pervasion component with member, ligthing paraphernalia (for example organic EL, LED), especially is suitable as the front diffused component of collimated back front diffusion system.
[main element symbol description]
10 matrix
11 resinous principles
20 light diffusing particulates
30 concentration adjustment districts
100 light diffusion elements
110 polaroids
120 protective seams
130 protective seams
200 polarization plates with light diffusion element
500 liquid crystal indicators

Claims (8)

1. the manufacture method of a light diffusion element, it comprises following operation:
Make the matrix of the precursor that contains resinous principle and ultra micron composition form material and the contacted operation of light diffusing particulate;
Make at least a portion of this precursor infiltrate into the operation of the inside of this light diffusing particulate; With
Polymerization occurs and forms the matrix that contains resinous principle and ultra micron composition in precursor simultaneously that make the precursor of the inside that infiltrates into this light diffusing particulate and do not infiltrate into this light diffusing particulate, simultaneously in the inner operation that forms the concentration adjustment district of the near surface of this light diffusing particulate;
At n AThe refractive index of the resinous principle of expression matrix, n BThe refractive index of expression ultra micron composition, n PWhen representing the refractive index of light diffusing particulate, | n P-n A| be 0.01～0.10, | n P-n B| be 0.10～1.50,
It is the compound of homology that described resinous principle contains with the light diffusing particulate.。
2. the manufacture method of light diffusion element as claimed in claim 1, wherein,
In described infiltration operation, make described precursor infiltrate into the scope below 95% more than 10% of the mean grain size of this light diffusing particulate from the surface of described light diffusing particulate.
3. the manufacture method of light diffusion element as claimed in claim 1 or 2, wherein,
Make the precursor of described resinous principle contact longer time of time till the particle diameter of this light diffusing particulate reaches in fact maximum with described light diffusing particulate.
4. the manufacture method of light diffusion element as claimed in claim 1 or 2, wherein,
Described resinous principle is ionization ray solidified resin, makes the precursor generation polymerization of this resinous principle by irradiation ionization property ray.
5. the manufacture method of light diffusion element as claimed in claim 3, wherein,
Described resinous principle is ionization ray solidified resin, makes the precursor generation polymerization of this resinous principle by irradiation ionization property ray.
6. light diffusion element, it is the light diffusion element that obtains by the described method of any one in claim 1 to 5, wherein,
Have the matrix that contains resinous principle and ultra micron composition and be scattered in light diffusing particulate in this matrix,
Has the concentration adjustment district that is formed by this resinous principle infiltration in the near surface inside of this light diffusing particulate.
7. manufacture method with the polarization plates of light diffusion element, its right to use requires the manufacture method of the described light diffusion element of any one in 1 to 5.
8. the manufacture method of a liquid crystal indicator, its right to use requires the manufacture method of the described light diffusion element of any one in 1 to 5.
CN2010800125331A 2009-03-26 2010-03-15 Process for producing light-diffusing element, light-diffusing element, and processes for producing polarizing plate with light-diffusing element and liquid-crystal display device Expired - Fee Related CN102356335B (en)

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