CN104871050B - Antiglare polarizing plate and image display device - Google Patents

Antiglare polarizing plate and image display device Download PDF

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Publication number
CN104871050B
CN104871050B CN201380066524.4A CN201380066524A CN104871050B CN 104871050 B CN104871050 B CN 104871050B CN 201380066524 A CN201380066524 A CN 201380066524A CN 104871050 B CN104871050 B CN 104871050B
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China
Prior art keywords
polarizing plate
spatial frequency
convex
dazzling
film
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CN201380066524.4A
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CN104871050A (en
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福井仁之
古谷勉
羽场康弘
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/408—Matt, dull surface
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

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

Abstract

An antiglare polarizing plate which includes both a polarizing film that comprises a polyvinyl alcohol-based resin and an antiglare layer formed on the polarizing film and which exhibits a total haze of 1% or less and has a thickness of 100[mu]m or less, characterized in that: the antiglare layer is provided with a fine rugged surface having fine ruggedness on the side opposite to the polarizing film; and the second derivative of common logarithm of one-dimensional power spectrum (H2(f)) of height of the fine rugged surface with respect to spatial frequency (f), d2logH2(f)/df2, is less than 0 at a spatial frequency of 0.01[mu]m-1, and larger than 0 at a spatial frequency of 0.02[mu]m-1.

Description

Anti-dazzling polarizing plate and image display device
Technical field
The present invention relates to anti-dazzling polarizing plate and use its image display device.
Background technology
For liquid crystal display or plasm display panel, Braun tube (cathode ray tube：CRT) display, have For the image display devices such as organic electro luminescent (EL) display, can significantly damage it if ambient light mirrors its display surface can Depending on property.In the past, in order to prevent mirroring for this kind of ambient light, in the television set or PC, the room of external light intensity of paying attention to image quality In the outer video camera for using or digital camera, the mobile phone shown using reflected light etc., in order to prevent reflecting for ambient light Enter and used anti-dazzling polarizing plate on the surface of image display device.
For anti-dazzling polarizing plate, it is desirable to anti-glare, show when the surface of image display device is configured at it is good Contrast, suppresses the generation of so-called " whiting ", " whiting " to be when the surface of image display device is configured at because of scattering Light and make whole display surface turn white, display is changed into muddy color, furthermore it is required that on the surface for being configured at image display device When suppress the generation of so-called " twinkling ", the pixel that " twinkling " is image display device is recessed with the surface of anti-dazzling polarizing plate Convex form is interfered, and is as a result produced Luminance Distribution and is difficult to watch.
In patent documentation 1 (Japanese Unexamined Patent Publication 2010-224427 publications), a kind of anti-dazzling polarizing plate is disclosed, it is shape Into the anti-dazzling polarizing plate of the antiglare layer with fine convex-concave surface, the work(of the absolute altitude by controlling micro concavo-convex surface Rate is composed, it is possible to obtain the anti-dazzling polarizing plate of anti-dazzle excellent performance.Specifically, following content is disclosed, i.e. by preventing 0.01 μm of the spatial frequency of the absolute altitude on the micro concavo-convex surface of dizzy property polarization plates- 1The power spectrum H at place1 2With the μ of spatial frequency 0.04 m- 1The power spectrum H at place2 2Ratio H1 2/H2 2It is set in the range of 3～15, it is possible to obtain with enough anti-glares and twinkling suppression The anti-dazzling polarizing plate of the excellent performances such as system.
For the anti-dazzling polarizing plate disclosed in patent documentation 1, by by the work(of the absolute altitude on its micro concavo-convex surface The ratio H of rate spectrum1 2/H2 2It is set in the range of 3～15, so as to the fluctuating of the surface unevenness profile with more than 50 μm of cycle subtracts It is few, can effectively suppress twinkling.However, in order to show good contrast and suppress the generation of whiting, as anti-glare The mist degree of one of the optical characteristics of polarization plates is the smaller the better, but when by anti-dazzling polarizing plate low haze, is connected with and helps table The fluctuating for revealing the surface unevenness profile with the cycle near 100 μm of anti-glare is also reduced, and anti-glare is possible to become not Fully.
Like this, although anti-glare, the performance of good contrast, the suppression of the generation of whiting and twinkling generation Suppression can be realized using the method described in patent documentation 1, but in the raising for further contrast and whiting The suppression of generation and make mist degree reduce in the case of, anti-glare will be reduced.In addition, further developing High precision is configured at Image display device in when be also possible to produce dazzle.
It should be noted that in order to solve the problems, such as that the anti-glare is not enough, it may be considered that following method：In antiglare layer Forming anti-reflection layer (for example, can enumerate transparent supporting mass/antiglare layer/low-index layer or transparent supporting mass/antiglare layer/height Index layer/low-index layer etc. is constituted), the deficiency of anti-glare is made up using the reduction of reflectance.However, in antiglare layer In the case of forming anti-reflection layer, need to form the anti-reflection layer with uniform thickness, therefore cost uprises.In addition, anti- In the case that the uniformity of the thickness in reflecting layer is insufficient, the problem for producing the not good situation in unequal quality is had.
On the other hand, dazzle to solve the problems, such as to eliminate, it may be considered that the method for giving internal haze to antiglare layer.So And the internal haze imparting to antiglare layer can be such that contrast significantly reduces.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2010-224427 publications
The content of the invention
Invent problem to be solved
Even it is an object of the present invention to provide a kind of low haze can also realize enough anti-glares and twinkling suppression The anti-dazzling polarizing plate of system.
For the method for solve problem
Have made intensive studies to solve the above problems, as a result the inventors discovered that：If the concave-convex surface of antiglare layer Shape is while the fluctuating with the cycle near 100 μm so that the fluctuating in the cycle near 50 μm is reduced, it is possible to low Enough anti-glares are shown during mist degree, while suppressing to dazzle.It has further been found that：By reducing liquid crystal image display device The thickness of distance, i.e. reduction anti-dazzling polarizing plate between the pattern of light filter etc. and micro concavo-convex surface (specifically will be anti- The thickness of dizzy property polarization plates is set to less than 100 μm), so as to will not also produce rolling when the image display device of fine is configured at Eye.The present inventor completes the present invention based on the opinion.
That is, the present invention is a kind of anti-dazzling polarizing plate, it is characterised in that be inclined comprising what is be made up of polyvinyl alcohol resin Vibrating diaphragm and the antiglare layer being formed on the polarizing coating, total mist degree is less than 1%, and thickness is that less than 100 μm of anti-glare is inclined Vibration plate,
The antiglare layer possesses with fine concavo-convex micro concavo-convex surface in the side contrary with the polarizing coating,
The One-dimensional power spectrum H of the absolute altitude on the micro concavo-convex surface2The common logarithm of (f) with regard to the two of spatial frequency f Order derivative d2logH2(f)/df2In 0.01 μm of spatial frequency- 1Place is less than 0, in 0.02 μm of spatial frequency- 1Place is more than 0.
In the micro concavo-convex surface, preferred angle is that the ratio in more than 5 ° of small face is less than 1%.
The maximum cross-section height Rt on the micro concavo-convex surface is preferably less than more than 0.3 μm 1 μm.
In addition, the invention further relates to a kind of image display device, it is characterised in that with the contrary of the micro concavo-convex surface Side configures above-mentioned anti-dazzling polarizing plate with the opposite mode of liquid crystal cell.
The effect of invention
Even according to the present invention it is possible to providing low haze can also realize that enough anti-glares are anti-with twinkling suppression Dizzy property polarization plates.
In addition, distance between the pattern of the light filter etc. by reducing liquid crystal image display device and micro concavo-convex surface, Reduce the thickness of anti-dazzling polarizing plate, such that it is able to further suppress to dazzle.
In addition, in the present invention, due to anti-reflection layer etc. need not be additionally formed in antiglare layer, therefore being not result in cost Raise, can suppress not good in the unequal quality of generation in the case where the uniformity of the thickness of anti-reflection layer etc. is insufficient Situation.
Description of the drawings
Fig. 1 is the profile of of the anti-dazzling polarizing plate for schematically showing the present invention.
Fig. 2 is the axonometric chart of of the anti-dazzling polarizing plate for schematically showing the present invention.
Fig. 3 is the schematic diagram of the state for representing function h (x, y) for discretely obtaining representing absolute altitude.
Fig. 4 is the mark on the micro concavo-convex surface of the anti-dazzling polarizing plate that the present invention is represented with discrete function h (x, y) of two dimension High figure.
Fig. 5 is illustrated two-dimensional power spectrum H2(fx, fy) with frequency space in the side equalized apart from f away from origin The schematic diagram of method.
Fig. 6 is that the absolute altitude for representing the micro concavo-convex surface to the anti-dazzling polarizing plate shown in Fig. 4 carries out discrete Fourier change The common logarithm logH of One-dimensional power spectrum obtained by changing2The figure of (f).
Fig. 7 is the schematic diagram for illustrating the assay method at the angle of inclination on micro concavo-convex surface.
Fig. 8 is histogrammic the one of the angle of inclination distribution in the small face on the micro concavo-convex surface for representing anti-dazzling polarizing plate The chart of example.
Fig. 9 is preferred of the first half of the manufacture method for schematically showing micro concavo-convex shape die for forming Figure.
Figure 10 is preferred of the latter half of the manufacture method for schematically showing micro concavo-convex shape die for forming Figure.
Figure 11 is the figure for representing the pattern used during the Mold Making of embodiment 1,2 and comparative example 1,2.
Figure 12 is to represent to carry out the pattern shown in Figure 11 power spectrum G obtained by discrete Fourier transform (DFT)2The figure of (f).
Figure 13 is the conventional right of the One-dimensional power spectrum of the absolute altitude calculating for representing the anti-dazzling polarizing plate according to embodiment 1 and 2 Number logH2The figure of (f).
Figure 14 is the conventional right of the One-dimensional power spectrum of the absolute altitude calculating for representing the anti-dazzling polarizing plate according to comparative example 1 and 2 Number logH2The figure of (f).
Figure 15 is the figure for representing the pattern used during the Mold Making of comparative example 3.
Figure 16 is the common logarithm for representing the One-dimensional power spectrum that the absolute altitude of the anti-dazzling polarizing plate according to comparative example 3 is calculated logH2The figure of (f).
Specific embodiment
The anti-dazzling polarizing plate of the present invention is comprising the polarizing coating being made up of polyvinyl alcohol resin and is formed at the polarizing coating On antiglare layer, total mist degree be less than 1%.Herein, total mist degree of anti-dazzling polarizing plate is determined as shown below.On polarizing coating After forming antiglare layer, to make not formed in the way of antiglare layer side becomes composition surface of polarizing coating, by anti-dazzling polarizing plate and glass Glass substrate is fitted with clear binder, and mist degree is determined according to JIS K 7136 from glass substrate side incident light.So determine Total mist degree of the mist degree equivalent to anti-dazzling polarizing plate.
The antiglare layer of the present invention is characterised by, possesses with fine concavo-convex fine in the side contrary with polarizing coating Convex-concave surface, the One-dimensional power spectrum H of the absolute altitude on micro concavo-convex surface described later2The common logarithm of (f) with regard to spatial frequency f Second dervative d2logH2(f)/df2In 0.01 μm of spatial frequency- 1Place is less than 0, in 0.02 μm of spatial frequency- 1Place is more than 0.This Bright anti-dazzling polarizing plate has excellent anti-glare and high twinkling rejection because having this kind of antiglare layer.
Additionally, being possible to slightly observe when the nearest High precision further image display device of development is configured at To dazzle, therefore present inventor has performed further investigation, as a result find：If the thickness of anti-dazzling polarizing plate is set to into 100 μm Hereinafter, even if then when the image display device of fine is configured at, it is also possible to be adequately suppressed twinkling.
Specifically, it is considered as pixel of the surface unevenness profile because of anti-dazzling polarizing plate with image display device to dazzle Produce Deng the interference of pattern.By the way that the thickness of anti-dazzling polarizing plate is set to into less than 100 μm, the pattern and surface unevenness profile The distance between will shorten.The inventors discovered that, shorten the distance, then can more suppress twinkling.
Herein, anti-dazzling polarizing plate of the invention at least has the polarizing coating being made up of polyvinyl alcohol resin and possesses Antiglare layer with fine concavo-convex micro concavo-convex surface.In addition, in general, polarization plates are with aobvious for being pasted on image Adhesive phase, optical compensating layer, optical compensation films, protecting film of showing device etc., and the anti-dazzling polarizing plate of the present invention is so-called " thickness " refers to the gross thickness of these all of layers and thin film.
The all of layer of the anti-dazzling polarizing plate of the present invention and the gross thickness of thin film are less than 100 μm.The present inventor's In result of study, because gross thickness is more thin, can more effectively suppress twinkling, therefore the gross thickness of anti-dazzling polarizing plate is more excellent Elect less than 90 μm, more preferably less than 80 μm as.Although the lower limit of the gross thickness of the anti-dazzling polarizing plate of the present invention does not have It is particularly limited to, yet with when gross thickness is thinning, as the mechanical strength of polarization plates the trend of reduction is just had, therefore from true From the viewpoint of protecting mechanical strength, preferably more than 50 μm.
＜ polarizing coating ＞
Polarizing coating used by anti-dazzling polarizing plate of the invention is illustrated.In the present invention, using by uniaxial tension Polyvinyl alcohol resin thin film in the gas absorption quantity polarizing coating of dichroism pigment.Constitute the polyethenol series tree of polarizing coating Fat is by the way that polyvinyl acetate system resin saponification is obtained.As polyvinyl acetate system resin, except as acetic acid second Beyond the polyvinyl acetate of the homopolymer of alkene ester, vinyl acetate can also be exemplified and can be copolymerized therewith others it is single Copolymer of body etc..As the other monomers with vinyl acetate copolymerization, for example, can enumerate unsaturated carboxylic acid class, alkene Class, vinyl ethers, unsaturated sulfonic acid class etc..The saponification degree of polyvinyl alcohol resin is usually 85～100 moles of %, preferably The scope of 98～100 moles of %.The polyvinyl alcohol resin can also be further modified, for example, it is also possible to using Jing aldehydes The polyvinyl formal being modified or polyvinyl acetal etc..The degree of polymerization of polyvinyl alcohol resin is usually 1000～ 10000, preferably 1500～10,000 scope.
Polarizing coating used by the present invention is through by the operation of this kind of polyvinyl alcohol resin thin film uniaxial tension, by poly- second Enol based resin film dichroism pigment dyes and makes the operation of the dichroism pigment absorption, will be adsorbed with dichroism pigment The operation of polyvinyl alcohol resin thin film boric acid aqueous solution process, the work washed in the laggard water-filling of process by boric acid aqueous solution Sequence and manufacture.
Uniaxial tension both can be carried out before the dyeing by dichroism pigment, it is also possible to by dichroism pigment Dyeing is simultaneously carried out, can be carrying out after the dyeing by dichroism pigment.After the dyeing by dichroism pigment In the case of carrying out uniaxial tension, the uniaxial tension both can be carried out in boric acid before processing, it is also possible to be carried out in boric acid process. In addition, uniaxial tension can certainly be carried out in above-mentioned multiple stages.When uniaxial tension is carried out, both can be in circumference speed Uniaxial tension between degree different roller, it is also possible to using hot-rolling uniaxial tension.In addition, both can be stretched in an atmosphere dry The wet tensile that formula is stretched, or stretched in the state of using solvent swell.Stretching ratio is usually 4～8 Times or so.
When polyvinyl alcohol resin thin film is dyeed with dichroism pigment, for example, as long as polyvinyl alcohol resin is thin Film immersion is in the aqueous solution containing dichroism pigment.As dichroism pigment, specifically can be using iodine or two colors Property dyestuff.
In the case where iodine is used as dichroism pigment, it is typically employed in the aqueous solution containing iodine and potassium iodide and soaks Stain polyvinyl alcohol resin thin film and the method that dyes.The content of the iodine in the aqueous solution is usually in every 100 weight portion water 0.01～0.5 weight portion or so, the content of potassium iodide is usually 0.5～10 weight portion or so in every 100 weight portion water.This is water-soluble The temperature of liquid is usually 20～40 DEG C or so, in addition, the dip time in the aqueous solution is usually 30～300 seconds or so.
On the other hand, in the case where dichroic dye is used as dichroism pigment, it is typically employed in containing water-soluble Property dichroic dye aqueous solution in impregnate polyvinyl alcohol resin thin film and the method that dyes.Dichromatic dye in the aqueous solution The content of material is usually 0.001～0.01 weight portion or so in every 100 weight portion water.The aqueous solution can also be containing sodium sulfate etc. Inorganic salt.The temperature of the aqueous solution is usually 20～80 DEG C or so, in addition, the dip time in the aqueous solution be usually 30～ 300 seconds or so.
Process by the boric acid after the dyeing of dichroism pigment, be the polyvinyl alcohol resin thin film by being colored It is immersed in boric acid aqueous solution and carries out.The content of the boric acid in boric acid aqueous solution is usually 2～15 weights in every 100 weight portion water Amount part or so, preferably 5～12 weight portions or so.In the case where iodine is used as dichroism pigment, the boric acid aqueous solution Preferably comprise potassium iodide.It is left that the content of the potassium iodide in boric acid aqueous solution is usually 2～20 weight portions in every 100 weight portion water The right side, preferably 5～15 weight portions.Dip time in boric acid aqueous solution is usually 100～1200 seconds or so, and preferably 150 ～600 seconds or so, more preferably 200～400 seconds or so.The temperature of boric acid aqueous solution is usually more than 50 DEG C, preferably 50～ 85℃。
Polyvinyl alcohol resin thin film after boric acid process generally carries out washing process.Washing process is, for example, by by boron Acid-treated polyvinyl alcohol resin is thin film dipped to be carried out in water.Implement dried after washing, obtain polarizing coating.Water The temperature of the water washed in processing is usually 5～40 DEG C or so, and dip time is usually 2～120 seconds or so.Drying followed by Process is usually used air drier or far infra-red heater and carries out.Baking temperature is usually 40～100 DEG C.Dried Process time is usually 120～600 seconds or so.
The polarizing coating that the polyvinyl alcohol resin thin film of iodine or dichroic dye is constituted thus has been obtained by gas absorption quantity. The thickness of the polarizing coating is preferably in the range of 5 μm～30 μm.It is possible without in the case where the thickness of polarizing coating is less than 5 μm Enough optical characteristics are shown, and mechanical strength is also possible to deficiency, therefore it is not preferred.On the other hand, in polarizing coating Thickness more than 30 μm in the case of, the gross thickness of anti-dazzling polarizing plate is possible to more than 100 μm, as a result, be possible to produce It is raw to dazzle therefore not ideal enough.
＜ antiglare layers ＞
(power spectrum of the absolute altitude on micro concavo-convex surface)
First, the power spectrum of the absolute altitude on the micro concavo-convex surface of antiglare layer is illustrated.Fig. 1 is to schematically show this The profile on the surface of the anti-dazzling polarizing plate of invention.As shown in figure 1, the anti-dazzling polarizing plate 1 of the present invention has polarizing coating 101 With the antiglare layer 102 being formed thereon, antiglare layer 102 possesses with fine concavo-convex 2 in the side contrary with polarizing coating 101 Micro concavo-convex surface.
Herein, so-called " absolute altitude on micro concavo-convex surface " described in the present invention is referred to：The surface of anti-dazzling polarizing plate 1 appoint (used as benchmark, absolute altitude is 0 μ to imaginary plane 103 at the point P of meaning and the average height on micro concavo-convex surface with the height M) air line distance on the principal normal direction 5 (normal direction of above-mentioned imaginary plane 103) of anti-dazzling polarizing plate.
Actually anti-dazzling polarizing plate is as schematically illustrated in Figure 2, fine concavo-convex with defining on two dimensional surface Antiglare layer.Therefore, micro concavo-convex surface absolute altitude as shown in Fig. 2 with (x, y) represent pellicular front in orthogonal coordinates when, The absolute altitude on micro concavo-convex surface can be expressed as two-dimensional function h (x, y) of coordinate (x, y).
The absolute altitude on micro concavo-convex surface can be according to using confocal microscope, interference microscope, atomic force microscope Etc. (AFM) three-dimensional information of the surface configuration that device is determined is obtained.Horizontal resolution required by measuring machine is at least 5 μm with Under, preferably less than 2 μm, in addition vertical resolution be at least less than 0.1 μm, preferably less than 0.01 μm.As being suitable to the survey Fixed non-contact three-dimensional surface configuration roughness measuring machine, can enumerate the series (Zygo of New View 5000 Corporation company systems, can buy from Zygo (strain) in Japan), three-dimensional microscope PL μ 2300 (Sensofar company systems) Deng.Because the resolution of the power spectrum of absolute altitude is needed for 0.005 μm- 1Hereinafter, thus determine area be preferably at least set to 200 μm More than × 200 μm, more than 500 μm of more preferably 500 μ m.
Below, the method to being obtained the power spectrum of absolute altitude using two-dimensional function h (x, y) is illustrated.First, using two dimension Function h (x, y), the two-dimension fourier transform defined by formula (1) obtains two-dimensional function H (fx, fy)。
[number 1]
Formula (1)
F hereinxAnd fyThe respectively frequency in x directions and y directions, the dimension reciprocal with length.In addition, in formula (1) π is pi, and i is imaginary unit.As the two-dimensional function H (f by obtained byx, fy) square, two-dimensional power spectrum H can be obtained2 (fx, fy).Two-dimensional power spectrum H2(fx, fy) represent antiglare layer micro concavo-convex surface spatial frequency distribution.
Hereinafter, in particular the method to obtaining the two-dimensional power spectrum of the absolute altitude on the micro concavo-convex surface of antiglare layer is carried out It is bright.Using the three-dimensional letter of the surface configuration of the practical measurements such as above-mentioned confocal microscope, interference microscope, atomic force microscope Breath is usually to be worth to as discrete, i.e., obtain as absolute altitude corresponding with multiple measuring points.Fig. 3 is to represent discretely obtain Represent the schematic diagram of the state of function h (x, y) of absolute altitude.If as shown in figure 3, represented in the face of antiglare layer just with (x, y) Hand over coordinate, the line dotted line split every Δ y by the line split every Δ x in x-axis direction and in y-axis direction on perspective plane 3 Represent, then in actual measure the absolute altitude on micro concavo-convex surface as the discrete of each intersection point of each dotted line on perspective plane 3 Absolute altitude is worth to.
The quantity of the absolute altitude value of gained is determined by measurement range and Δ x and Δ y, if as shown in Figure 3 by the survey in x-axis direction Determine scope and be set to X=(M-1) Δ x, the measurement range in y-axis direction is set to into Y=(N-1) Δ y, then the number of the absolute altitude value of gained Measure as M × N number of.
If be as shown in Figure 3 set on the coordinate of starting point A on perspective plane 3, ((herein j is more than 0 to j Δ x, k Δ y) Below M-1, k are more than 0 below N-1.), then the absolute altitude of the point P on pellicular front corresponding with starting point A can be expressed as h (j Δ x, k Δ y).
Herein, measuring interval Δ x and Δ y depend on the horizontal resolution of mensuration machine, in order to precision evaluates well micro- Thin convex-concave surface, as described above, it is preferred to Δ x and Δ y are less than 5 μm, more preferably less than 2 μm.In addition, measurement range X and Y It more preferably all it is more than 500 μm as described above, it is preferred to all be more than 200 μm.
Like this, in actual measure, the function for representing the absolute altitude on micro concavo-convex surface is as with M × N number of Discrete function h (x, y) of value is obtained.The discrete Fourier defined by discrete function h (x, y) obtained by measure and by formula (2) Leaf transformation obtains discrete function H (fx, fy), by by discrete function H (fx, fy) square and obtain the discrete letter of two-dimensional power spectrum Number H2(fx, fy).L in formula (2) is the integer below-M/2 above M/2, and m is the integer below-N/2 above N/2.In addition, ΔfxAnd Δ fyIt is respectively the frequency interval in x directions and y directions, is defined by formula (3) and formula (4).
[number 2]
Formula (2)
[number 3]
Formula (3)
[number 4]
Formula (4)
Herein, as shown in figure 4, because the micro concavo-convex surface of antiglare layer is randomly formed concavo-convex, therefore frequency space is (empty Between frequency field) in two-dimensional power spectrum H2(fx, fy) with origin (fx=0, fy=0) centered in symmetrical.Therefore, two-dimensional function H2(fx, fy) can be transformed to frequency space in away from origin apart from f (units：μm- 1) as the one-dimensional functions H of parameter2 (f).For the antiglare layer used by the anti-dazzling polarizing plate of the present invention, by one-dimensional functions H2F One-dimensional power that () represents Spectrum has certain feature.
Specifically, first, as shown in Figure 5 in frequency space, calculate and be located at and origin O (fx=0, fy=0) apart (n-1/2) numbers Nn of the Δ f less than all of point (bullet in Fig. 5) at the distance of (n+1/2) Δ f.Fig. 5 In shown example, Nn=16.Then, calculate and be located at origin O at a distance of (n-1/2) Δ f less than (n+1/2) Δ f Distance at all of point H2(fx, fy) aggregate value H2N (the H of the bullet in Fig. 52(fx, fy) aggregate value), such as formula (5) shown in, with aggregate value H2N divided by point number Nn, using the value of gained as H2The value of (f).
[number 5]
Formula (5)
Herein, in the case of M >=N, n is the integer of more than 0 below N/2, and in the case of M ＜ N, n is more than 0 M/2 Following integer.It should be noted that M and N is as shown in figure 3, refer respectively to number and the y-axis direction of the measuring point in x-axis direction Measuring point number.In addition, Δ f is set to (Δ fx+Δfy)/2。
In general, the One-dimensional power spectrum obtained using described method includes noise when determining.This is in asks one-dimensional During power spectrum, in order to eliminate the effect of noise, the absolute altitude on the preferred micro concavo-convex surface for determining the multiple positions in antiglare layer, The meansigma methodss that the One-dimensional power obtained according to the absolute altitude on each micro concavo-convex surface is composed compose H as One-dimensional power2F () uses. The number at the position being measured to the absolute altitude on the micro concavo-convex surface in antiglare layer is preferably more than 3 positions, and more preferably 5 It is more than individual position.
In Fig. 6, the common logarithm logH of the One-dimensional power spectrum of the absolute altitude on the micro concavo-convex surface so tried to achieve is shown2(f)。 The common logarithm logH of the One-dimensional power spectrum of Fig. 62F (), is to the fine recessed of the different parts according to 5 positions in antiglare layer One-dimensional power that the absolute altitude of nonreentrant surface is obtained spectrum carry out it is average obtained by.
The logarithm logH of the One-dimensional power spectrum of the absolute altitude on micro concavo-convex surface2The second dervative with regard to spatial frequency f of (f) d2logH2(f)/df2The common logarithm logH that can be composed by One-dimensional power2F () is calculating.Specifically, it is possible to use formula (6) Calculus of finite differences calculate second dervative.
[number 6]
Formula (6)
The common logarithm logH of the One-dimensional power spectrum of the absolute altitude shown in Fig. 62The second dervative with regard to spatial frequency f of (f) d2logH2(f)/df2In 0.01 μm of spatial frequency- 1Locate as -11878, in 0.02 μm of spatial frequency- 1Locate as 8081.Therefore, from It will be clear that the common logarithm logH that the One-dimensional power of absolute altitude is composed in Fig. 62F () is used as relative to spatial frequency Chart when intensity is represented is in 0.01 μm of spatial frequency- 1Place has convex shape, in 0.02 μm of spatial frequency- 1Place has Downward convex shape.
The antiglare layer of anti-dazzling polarizing plate of the present invention is characterised by, by the absolute altitude on micro concavo-convex surface calculate it is one-dimensional The common logarithm logH of power spectrum2Second dervative d with regard to spatial frequency f of (f)2logH2(f)/df2In the μ of spatial frequency 0.01 m- 1Place is less than 0, in 0.02 μm of spatial frequency- 1Place is more than 0.As a result, one-dimensional by what is calculated by the absolute altitude on micro concavo-convex surface The common logarithm logH of power spectrum2(f) as spatial frequency f function representation when chart in 0.01 μm of spatial frequency- 1Place's tool There is convex shape, in 0.02 μm of spatial frequency- 1Place has shape convex downwards, and the surface unevenness profile of antiglare layer is effective Ground has contributes to 100 μm of antiglare effect or so in low haze (equivalent to 0.01 μm in spatial frequency- 1) cycle Fluctuating, and efficiently reduce 50 μm nearby (equivalent to 0.02 μm in spatial frequency- 1) cycle fluctuating.
(angle of inclination on micro concavo-convex surface)
In addition, the inventors discovered that, in the antiglare layer of anti-dazzling polarizing plate, if constituting each micro- of micro concavo-convex surface Facet shows specific angle of inclination distribution, then can be general being effectively prevented while excellent anti-dazzle performance is shown White aspect is more efficient.That is, in the micro concavo-convex surface of antiglare layer, preferred angle is the ratio in more than 5 ° of small face Less than 1%.If the ratio that the angle of inclination in micro concavo-convex surface is more than 5 ° of small face is more than 1%, convex-concave surface The precipitous small face in angle of inclination become many, will be from the light optically focused of surrounding, the whiting that easily generation display surface integrally bleaches. In order to suppress this kind of spotlight effect, whiting is prevented, the angle of inclination in micro concavo-convex surface is the ratio in more than 5 ° of small face It is the smaller the better, preferably smaller than 0.5%, more preferably less than 0.1%.
Herein, " angle of inclination in the small face on micro concavo-convex surface " described in the present invention is referred to anti-shown in Fig. 2 At the arbitrary point P of the anti-glare layer surface of dizzy property polarization plates 1, incorporate the small face comprising point P as described later it is concavo-convex after Local normal 6 and anti-dazzling polarizing plate the angulation θ of principal normal direction 5.With regard to the inclination angle on micro concavo-convex surface Degree, identically with absolute altitude, can be by using the devices such as confocal microscope, interference microscope, atomic force microscope (AFM) measure The three-dimensional information of surface configuration obtain.
Fig. 7 is the schematic diagram for illustrating the assay method at the angle of inclination in the small face on micro concavo-convex surface.If right The determination method at specific angle of inclination is illustrated, then as shown in fig. 7, determining in imaginary plane FGHI being represented by dotted lines Starting point A, the vicinity of starting point A in the x-axis of crossing point A substantially symmetrically takes point B and D, exists in addition relative to point A The vicinity of starting point A in the y-axis of crossing point A, relative to point A point C and E is substantially symmetrically taken, it is determined that with these points B, C, D, E Point Q, R, S, T on corresponding anti-glare layer surface.It should be noted that in Fig. 7, being represented in the face of antiglare layer just with (x, y) Coordinate is handed over, with z the coordinate of antiglare layer thickness direction is represented.Plane FGHI is parallel to the straight of x-axis by the point C passed through in y-axis Line and the straight line parallel to x-axis and the straight line parallel to y-axis through the point B in x-axis similarly through the point E in y-axis, And the face for similarly being formed through respective intersection point F, G, H, I of the straight line parallel to y-axis of the point D in x-axis.In addition, though In the figure 7, relative to plane FGHI, by the position of actual anti-glare layer surface up in the way of describe, but according to having in mind Point A position takens are different, have the position of actual anti-glare layer surface certainly in the situation of the top of plane FGHI, also have under The situation of side.
Additionally, the angle of inclination of the surface profile data of gained can obtain as follows：To by the reality corresponding to starting point A Anti-glare layer surface on point P and corresponding to the point on the actual anti-glare layer surface of 4 point B, C, D, the E for being taken in its vicinity 4 planes of polygon of total 5 points of formation of Q, R, S, T, i.e., each normal vector 6a of 4 trianglees PQR, PRS, PST, PTQ, 6b, 6c, 6d are averaged, and obtain the polar angle of normal (vector) 6 of the local of gained (in Fig. 2, with angle formed by principal normal direction 5 Degree θ).After obtaining angle of inclination to each measuring point (small face), rectangular histogram is calculated.
Fig. 8 is the figure of histogrammic of the angle of inclination distribution in the small face on the micro concavo-convex surface for representing antiglare layer Table.In chart shown in Fig. 8, transverse axis is angle of inclination, is split with 0.5 ° of scale.For example, the vertical bar of the leftmost side represents inclination angle The distribution of set of the degree in 0～0.5 ° of scope, below, with advancing to the right, angle increases every time 0.5 °.In figure, in horizontal stroke Axle per 2 scales at expression value higher limit, for example, be denoted as in transverse axis " 1 " part represent angle of inclination be in 0.5～1 ° Scope small face set distribution.In addition, the longitudinal axis represents the overall ratio relative to the set, be add up to for 1 value.In the example, angle of inclination is the ratio substantially 0 in more than 5 ° of small face.
(surface roughness parameter on micro concavo-convex surface)
For the fine surface unevenness profile of antiglare layer, according to the arithmetic average roughness of the regulation of JIS B 0601 Ra is preferably less than more than 0.04 μm 0.1 μm.In addition, being preferably according to the maximum cross-section height Rt of the regulation of JIS B 0601 Less than more than 0.3 μm 0.6 μm.In addition, being preferably more than 50 μm 130 μm according to average length RSm of the regulation of JIS B 0601 Below.
In the case where arithmetic average roughness Ra is less than 0.04 μm, the anti-dazzle of antiglare layer obtained by its concaveconvex shape is transferred Property is possible to become insufficient.On the other hand, in the case where arithmetic average roughness Ra is higher than 0.1 μm, its concave-convex is transferred Antiglare layer obtained by shape may produce whiting.
In the case where maximum cross-section height Rt is less than 0.3 μm, the anti-glare of antiglare layer obtained by its concaveconvex shape is transferred It is possible to become insufficient.On the other hand, in the case where height Rt in maximum cross-section is higher than 0.6 μm, transfer its concaveconvex shape and The antiglare layer for obtaining is possible to produce whiting, and there is the uniformity reduction of surface unevenness profile and produce the possibility dazzled.
In addition, in the case where average length RSm is less than 50 μm, transferring the anti-glare of antiglare layer obtained by its concaveconvex shape It is possible to become insufficient.On the other hand, in the case where average length RSm is higher than 130 μm, transfer obtained by its concaveconvex shape Antiglare layer is possible to produce dazzles.
Manufacture method ＞ of ＜ antiglare layers
Above-mentioned antiglare layer both can be formed directly on polarizing coating, it is also possible to following to be formed, that is, be produced on transparent supporting The antiglare film of antiglare layer is defined on body, by the antiglare film by gluing oxidant layer in case the opposite side of dizzy layer side fits in polarization Film.
Antiglare layer can be made using the method including following operation, and the operation is：By being included in mould base material Surface formed based on the method for the operation of the surface configuration (micro concavo-convex) of predetermined pattern manufacturing micro concavo-convex formation mould Tool, by shape transfer of the male and fomale(M＆F) of manufactured mould to transparent resin film etc. after, by transferred with the male and fomale(M＆F) of mould The transparent resin film of shape is peeled off from mould.
In order to precision it is excellent form the micro concavo-convex surface of the antiglare layer with feature as above, preferably, with Chart when the One-dimensional power spectrum of the pattern of above-mentioned regulation is represented as the intensity relative to spatial frequency is in spatial frequency 0.007 μm- 10.015 μm of the above- 1Hereinafter there is 1 maximum, and in 0.05 μm of spatial frequency- 10.1 μm of the above- 1Hereinafter have 1 Individual maximum.Herein, so-called " pattern " refers to the view data for forming the micro concavo-convex surface of antiglare layer or with printing opacity Mask of portion and light shielding part etc..
Additionally, it is preferred that 0.007 μm of the spatial frequency of pattern used in the manufacture of micro concavo-convex shape die for forming- 1More than 0.015μm- 1The intensity of the first following maximum, less than 0.05 μm of spatial frequency- 10.1 μm of the above- 1Following second is very big The intensity of value.In the case where the intensity of the first maximum is more than the second maximum, dazzling has the trend for becoming strong, therefore unexcellent Choosing.
The two-dimensional power spectrum of pattern is obtained as follows：For example in the case where pattern is view data, view data is being become Be changed to 2 gray scale (Bands Tone) binary image data after, with two-dimensional function g (x, y) represent view data gray scale, to gained Two-dimensional function g (x, y) carries out Fourier transform, calculates two-dimensional function G (fx, fy), by the two-dimensional function G (f of gainedx, fy) flat Side.Herein, x and y represent the orthogonal coordinates in view data face, fxAnd fyRepresent the frequency in x directions and the frequency in y directions.
It is identical with the situation of the two-dimensional power spectrum of the absolute altitude on the micro concavo-convex surface for seeking antiglare layer, for the two dimension for seeking pattern The situation of power spectrum, two-dimensional function g (x, y) of gray scale is also generally to obtain as discrete function.In this case, with ask The situation of the two-dimensional power spectrum of the absolute altitude on micro concavo-convex surface is identical, as long as calculating two-dimensional power spectrum using discrete Fourier transform (DFT) .The One-dimensional power of pattern is composed by the two-dimensional power spectrum of pattern, to compose phase with the One-dimensional power of the absolute altitude on micro concavo-convex surface Same mode is obtained.
By using the One-dimensional power spectrum in the pattern for making antiglare layer in 0.007 μm of spatial frequency- 10.015 μm of the above- 1 Hereinafter there is the first maximum, in 0.05 μm of spatial frequency- 10.1 μm of the above- 1Hereinafter there is the second maximum, such that it is able to To using the absolute altitude on micro concavo-convex surface One-dimensional power spectrum common logarithm as the intensity relative to spatial frequency represent when Chart is in 0.01 μm of spatial frequency- 1Place has convex shape, in 0.02 μm of spatial frequency- 1Place has shape convex downwards Antiglare layer.
In order to make One-dimensional power spectrum in 0.007 μm of spatial frequency- 10.015 μm of the above- 1Hereinafter there is the first maximum value In 0.05 μm of spatial frequency- 10.1 μm of the above- 1Hereinafter there is the pattern of the second maximum, as long as through following band filter , i.e. from randomly collocation point and made by pattern, with using random number or by computer generate pseudo random number determine In the pattern of deep or light random Luminance Distribution, the band filter of the composition of specific spatial frequency range is removed.
Herein, the spatial frequency distribution on the micro concavo-convex surface of antiglare layer is properly formed preferably as described above.Therefore, it is excellent Choosing makes antiglare layer using following embossing, and the embossing is characterised by, is had using above-mentioned pattern manufacture fine The mould of convex-concave surface, the photo-curable tree male and fomale(M＆F) of manufactured mould being transferred on transparent supporting mass or on polarizing coating Lipid layer etc., then will peel off, thus at transparent transferred with the antiglare layer of male and fomale(M＆F) and transparent supporting mass or polarizing coating from mould Hold on body or make on polarizing coating antiglare layer.
Herein, as embossing, UV embossings using light-cured resin can be exemplified, using thermoplastic resin Heat embossing method, wherein, from from the viewpoint of productivity, preferred UV embossings.
UV embossings are, by forming light-cured resin layer on the surface of transparent supporting mass or polarizing coating, by the light Curable resin layer is allowed to solidify while pushing to the male and fomale(M＆F) of mould, thus the male and fomale(M＆F) of mould is transferred to into photo-curable The method of resin bed.Specifically, coated UV line gel-type resin on transparent supporting mass or on polarizing coating, makes to be coated with Ultraviolet curing resin and mould male and fomale(M＆F) it is closely sealed in the state of, from transparent supporting mass or polarizing coating side irradiation ultraviolet radiation And solidify ultraviolet curing resin, peel off the ultraviolet curing resin layer being formed with after solidification from mould thereafter (anti-dazzle Layer) transparent supporting mass or polarizing coating.
It is not particularly limited using the species of ultraviolet curing resin during UV embossings, it is possible to use commercially available is suitable Resin.Alternatively, it is also possible to using being combined with the light trigger for rightly selecting in ultraviolet curing resin, with than ultraviolet The resin that the longer visible ray of line wavelength can also solidify.Specifically, may be used alone trimethylolpropane tris The polyfunctional acrylic esters such as acrylate, tetramethylol methane tetraacrylate, or it is used in mixed way they two or more, it is also possible to Suitably use itself and Irgacure 907 (Ciba Specialty Chemicals company systems), Irgacure 184 The Photoepolymerizationinitiater initiater such as (Ciba Specialty Chemicals company systems), Lucirin TPO (BASF AG's system) mix and The material for obtaining.
On the other hand, heat embossing method is to push away the transparent supporting mass formed from thermoplastic resin to mould in a heated state Pressure, by the method for the transferring surface shape of mould to transparent supporting mass.As transparent supporting mass used in heat embossing method, as long as Substantially transparent supporting mass, then either which kind of material can, it is, for example possible to use polymethyl methacrylate, poly- Carbonic ester, polyethylene terephthalate, triacetyl cellulose, using norborene based compound as the amorphism ring of monomer Solvent cast film or extruded film of the thermoplastic resins such as shape polyolefin etc..These transparent resin films can also be used as described above UV embossings in the transparent supporting mass for coated UV line gel-type resin and suitably use.
(antiglare film)
As long as transparent supporting mass used is essentially optically transparent thin film when making antiglare film, for example can be with Enumerate triacetylcellulose film, pet film, polymethyl methacrylate film, Merlon thin Film, using norborene based compound as the solvent cast film or extrusion of the thermoplastic resins such as the noncrystalline cyclic polyolefin of monomer The resin films such as film.
The thickness of transparent supporting mass is preferably in the range of 10 μm～60 μm.10 μm are less than in the thickness of transparent supporting mass In the case of, mechanical strength is possible to not enough therefore not preferred.On the other hand, the thickness in transparent supporting mass is higher than 60 μm In the case of, the probability of the gross thickness of anti-dazzling polarizing plate more than 100 μm is uprised, as a result, be possible to produce dazzle, therefore It is not preferred.
In addition, as adhesive used when polarizing coating is fitted with antiglare film, it is possible to use known adhesive. The water soluble adhesive that make use of polyvinyl alcohol resin, the cationic polymerization that make use of epoxy system resin can for example be used Adhesive, make use of acrylic resin radical polymerization adhesive, make use of based on epoxy system resin and acrylic acid seriess The cationic polymerization of the mixture of resin and the adhesive of radical polymerization etc..The thickness of adhesive according to the species of adhesive and Difference, therefore cannot treat different things as the same, but in the range of preferably 0.1 μm～5 μm.0.1 μm is less than in the thickness of gluing oxidant layer In the case of, it is possible to enough adhesive strengths cannot be obtained, thus it is not preferred.On the other hand, in the thickness of gluing oxidant layer In the case of 5 μm, the probability of the gross thickness of anti-dazzling polarizing plate more than 100 μm is uprised, as a result, being possible to produce Dazzle, thus it is not preferred.
Manufacture method ＞ of ＜ micro concavo-convex shape die for forming
Hereinafter, to manufacturing to form the fine concavo-convex and mould that uses on the surface of antiglare layer, (micro concavo-convex is formed With mould) method illustrate.For the manufacture method of micro concavo-convex shape die for forming, as long as can obtain use The method of the surface configuration of the regulation of the pattern stated, is just not particularly limited, but in order to precision is excellent and repeatability is excellent Ground manufacture micro concavo-convex surface, preferably substantially includes：(1) first plating operation, (2) grinding step, (3) photosensitive resin film Formation process, (4) exposure process, (5) developing procedure, (6) first etching work procedures, (7) photosensitive resin film stripping process, (8) Second etching work procedure, (9) second plating operations.
Fig. 9 is preferred of the first half of the manufacture method for schematically showing micro concavo-convex shape die for forming Figure.The section of the mould in each operation is schematically shown in Fig. 9.Hereinafter, while with reference to Fig. 9, to the micro- of the present invention The each operation of the manufacture method of thin concave-convex die for forming is described in detail.
(1) first plating operation
In the manufacture method of micro concavo-convex shape die for forming, first, copper facing is implemented to the surface of base material (mould base material). By implementing copper facing to the surface of mould base material like this, such that it is able to improve the second plating operation below in chromium plating Adaptation, glossiness.Its reason is that copper-plated coating property is high, and in addition smoothing effect is strong, therefore can be by mould base material Small concavo-convex or pore etc. is filled and forms flat and glossiness surface.Using these copper-plated characteristics, even if aftermentioned The second plating operation in implement chromium plating, it is also possible to elimination be considered as because being present in mould base material in it is small concavo-convex or Pore and the cracking of chrome-plated surface that causes, further, since copper-plated coating property is high, therefore can reduce the product of tiny crackle It is raw.
As copper used in the first plating operation, in addition to it can be the simple metal of copper, can also be based on copper The alloy of body, thus, described " copper " is the implication for including copper and copper alloy in this specification.Copper facing both can using plating come Carry out, it is also possible to carried out using electroless plating, but generally using plating.
When copper facing is implemented, if coating is too thin, the impact of substrate surface cannot be completely excluded, therefore its thickness is preferred For more than 50 μm.The upper limit of thickness of coating does not have the limit, but from from the aspect of cost etc., it is however generally that to 500 μm or so i.e. Enough.
It should be noted that in the manufacture method of micro concavo-convex shape die for forming, as going for mould base The metal material of the formation of material, aluminum, ferrum etc. can be enumerated from from the viewpoint of cost.Additionally, consider from the convenience disposed, more It is preferred that the aluminum of lightweight.Herein described aluminum, ferrum again in addition to can be respectively beyond simple metal can also be using aluminum or ferrum as The alloy of main body.
As long as in addition, the appropriate shape adopted in the past in shape this area of mould base material, no spy Do not limit, both can be tabular, or cylindric or cylindric roller.If made of base material using the mould of roll Mould, then have the advantage that can manufacture anti-dazzling polarizing plate or antiglare film with continuous drum.
(2) grinding step
In ensuing grinding step, to implementing copper-plated mould base material in the first above-mentioned plating operation Surface is ground.In the manufacture method of micro concavo-convex shape die for forming, substrate surface is ground to preferably through the operation The state of close minute surface.Its reason is, for the metallic plate or metallic roll that become base material, in order to make required essence Degree, implements the machinings such as cutting, grinding more, thus will process lines (original text in the remained on surface of mould base material：Processing Mesh), even if in the state of copper facing has been carried out, the situation of these processing lines of residual is also had, in addition, carrying out plating In the state of, surface not necessarily fully smooths.That is, even if implementing aftermentioned to this kind of surface for remaining deep processing lines etc. Operation, also have processing lines etc. it is concavo-convex than implementing each operation after the concavo-convex deeper situation that formed, it is possible to residual adds The impact of work lines etc., it is special to optics sometimes in the case of using this kind of Making mold anti-dazzling polarizing plate or antiglare film Property cause expected to affect.In Fig. 9 (a), it is schematically shown：Flat mould base material 7 is in the first plating operation In its surface be carried out copper facing (for the copper-plated layer formed in the operation is not illustrated), had by grinding step then The state on the surface 8 having by mirror ultrafinish.
With regard to the method that the surface of the mould base material after to implementing copper facing is ground, it is not particularly limited, can be with Using mechanical milling method, electrolytic polishing method, chemical grinding method any one.As mechanical milling method, superfinishing can be exemplified Processing method, polishing processes, fluid polishing, polishing polishing etc..Alternatively, it is also possible to by the cutting element used in grinding step Mirror-finish cutting is carried out, and minute surface is made on the surface 8 of mould base material 7.Material, shape of cutting element now etc. are without spy Do not limit, it is possible to use superhard cutter, CBN cutters, sintex, diamond cutter etc., but examine from the viewpoint of machining accuracy Worry preferably uses diamond cutter.For the surface roughness after grinding, the centrage according to the regulation of JIS B 0601 is average Roughness Ra is preferably less than 0.1 μm, more preferably less than 0.05 μm.If the center line average roughness Ra after grinding is more than 0.1 μm, then the impact of the surface roughness after grinding is possible to the concaveconvex shape of the die surface for residuing in final, therefore not It is preferred that.In addition, the lower limit for center line average roughness Ra is not particularly limited, from process time, the viewpoint of processing cost Consider, naturally occurring has the limit, therefore need not specify.
(3) photosensitive resin film formation process
In ensuing photosensitive resin film formation process, photoresist is made the solution that is dissolved in solvent and is applied Cloth is heated, is dried, thus shape on surface 8 of the mould with base material 7 that mirror ultrafinish is implemented by above-mentioned grinding step Into photosensitive resin film.In Fig. 9 (b), it is schematically shown define photosensitive resin film 9 on the surface 8 of mould base material 7 State.
Known photoresist can be used as photoresist.For example, as with photographic department distribution life The photoresist of the minus of the property of solidification, it is possible to use the propylene with acryloyl group or methylacryloyl in the molecule Monomer or prepolymer, the mixture of double azido compound and diene rubber, poly- vinyl cinnamate based compound of acid esters etc..Separately Outward, as the photoresist using development with photosensitive part dissolution, the eurymeric of the property of only not photosensitive part residual, can With using phenolic resin system or novolac resin system etc..Alternatively, it is also possible to coordinate sensitization as needed in photoresist The various additives such as agent, development accelerant, adaptation modifying agent, coating modifying agent.
When these photoresists to be coated the surface 8 of mould base material 7, in order to form good film, preferably Coating after being diluted in appropriate solvent, it is possible to use cellosolve system solvent, Propylene Glycol system solvent, ester system solvent, alcohol system solvent, Ketone system solvent, highly polar solvent etc..
As the method for photosensitive resin coating solution, it is possible to use meniscus coating, spray coating, dip-coating, spin coating, roller The known method such as painting, wire drawing rod coating, airblade coating, scraper plate coating, curtain coating, ring type coating (リ Application グ U ー ト).Apply The thickness of cloth film is preferably set to 1～10 μm after drying of scope.
(4) exposure process
In ensuing exposure process, in the photoresist formed in above-mentioned photosensitive resin film formation process Following pattern is exposed on film 9, i.e. above-mentioned One-dimensional power is composed as the intensity relative to spatial frequency represent when chart In 0.007 μm of spatial frequency- 10.015 μm of the above- 1Hereinafter there is 1 maximum value and in 0.05 μm of spatial frequency- 1More than 0.1μm- 1Hereinafter there is the pattern of 1 maximum.As long as light source used and the photoresist being coated with exposure process Wavelength photoreceptor, sensitivity etc. are matchingly appropriate to be selected, it is, for example possible to use the g line (wavelength of high voltage mercury lamp：436nm), it is high H line (the wavelength of pressure mercury lamp：405nm), the i line (wavelength of high voltage mercury lamp：365nm), semiconductor laser (wavelength：830nm、 532nm, 488nm, 405nm etc.), YAG laser (wavelength：1064nm), KrF excimer laser (wavelength：248nm), ArF quasi-molecules Laser (wavelength：193nm), F2 excimer laser (wavelength：157nm) etc..
In the manufacture method of micro concavo-convex shape die for forming, in order to precision it is excellent form surface unevenness profile, expose In light operation, preferably above-mentioned pattern is set to expose on photosensitive resin film in the state of critically controlling.In micro concavo-convex shape In the manufacture method of die for forming, in order that above-mentioned pattern precision on photosensitive resin film exposes excellently, preferably： Make pattern on computer in the form of image data, using from the laser sent by the laser head of computer controls drawing base In the pattern of the view data.Carry out can be using the laser describing device of galley making when laser is drawn.As this Laser describing device is planted, for example, can enumerate Laser Stream FX ((strain) Think Laboratory systems) etc..
In Fig. 9 (c), it is schematically shown the state after having exposed pattern on photosensitive resin film 9.In the sense with minus In the case of photosensitiveness resin formation photosensitive resin film, the region 10 being exposed carries out the cross-linking reaction of resin because of exposure, Dissolubility in developer solution described later is reduced.Thus, the region 11 not being exposed in developing procedure is dissolved by the developing, only The region 10 being exposed remains on the surface of mould base material and becomes mask.On the other hand, in the photonasty tree with eurymeric In the case that fat forms photosensitive resin film, the region 10 being exposed cuts off the bonding of resin because of exposure, in development described later Dissolubility in liquid increases.Thus, the region 10 being exposed in developing procedure is dissolved by the developing, the region not only being exposed Become mask on 11 surfaces for residuing in mould base material.
(5) developing procedure
In ensuing developing procedure, in the case of the photoresist of minus used in photosensitive resin film 9, The region 11 not being exposed is dissolved by the developing, and the region 10 being only exposed is residued on mould base material, ensuing Play a role as mask in one etching work procedure.On the other hand, the photoresist of eurymeric used in photosensitive resin film 9 In the case of, the region 10 being only exposed is dissolved by the developing, and the region 11 not being exposed is remained on mould base material, as Mask in ensuing first etching work procedure plays a role.
For developer solution used in developing procedure can use known developer solution.For example, hydrogen-oxygen can be enumerated Change primary amine class, the diethyls such as inorganic base, ethamine, the n-propylamines such as sodium, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia The hydramine such as the tertiary amines such as the secondary amine classes such as amine, di-n-butylamine, triethylamine, methyidiethylamine, dimethylethanolamine, triethanolamine The rings such as quaternary ammonium salt, pyrroles, the piperidines such as class, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl hydroxyethylammonium hydroxide Organic solvents such as alkaline aqueous solution, dimethylbenzene, the toluene of shape amine etc. etc..
For the developing method in developing procedure is not particularly limited, it is possible to use immersion development, spray development, hairbrush show The methods such as shadow, supersonic wave development.
In Fig. 9 (d), it is schematically shown the photoresist of minus used in photosensitive resin film 9, developed The state of process.The region 11 not being exposed in Fig. 9 (c) is dissolved by the developing, and the region 10 being only exposed residues in mould Become mask 12 with the surface of base material.In Fig. 9 (e), it is schematically shown the sense of eurymeric used in photosensitive resin film 9 Photosensitiveness resin has carried out the state of development treatment.The region 10 being exposed in Fig. 9 (c) is dissolved by the developing, and is not only exposed Region 11 residues on the surface of mould base material and becomes mask 12.
(6) first etching work procedures
In ensuing first etching work procedure, by the surface that mould base material is remained in after above-mentioned developing procedure Photosensitive resin film is used as mask, and mainly the mould at maskless position is carried out with the surface for implementing plating of base material Etching.
Figure 10 is the figure of preferred of the latter half of the manufacture method of the mould for schematically showing the present invention.Figure The state with base material 7 by the mould in the maskless region 13 of the first etching work procedure main etch is schematically shown in 10 (a). The mould of the bottom of mask 12 base material 7 not by from the surface of mould base material etching, however as etching carrying out, never The etching for having 13, the region of mask is constantly carried out.Thus, near the boundary in mask 12 with maskless region 13, mask 12 The mould base material 7 of bottom be also etched.Below by this kind of near the boundary in mask 12 with maskless region 13, mask Also etched situation is referred to as side etching to the mould base material 7 of 12 bottom.
Etch processes in first etching work procedure are typically by using iron chloride (FeCl3) liquid, copper chloride (CuCl2) liquid, Alkali etching liquid (Cu (NH3)4Cl2) etc. corrosion metal surface carrying out, but can also be using strong acid such as hydrochloric acid, sulphuric acid, can be with Using the reverse electrolysis etching carried out by applying the current potential contrary with during plating.Mould is formed at when implementing etch processes Concave shape with base material is different according to the species of base metal, the species of photosensitive resin film and etching maneuver etc., it is impossible to one In general, but in the case where etch quantity is less than 10 μm, by substantially respectively to same from the metal surface contacted with etching solution Property ground etching.Herein described etch quantity is the thickness of the mould base material being shaved because of etching.
Etch quantity in first etching work procedure is preferably 1～50 μm, more preferably 2～10 μm.1 μm is less than in etch quantity In the case of, concaveconvex shape is not substantially formed in metal surface, become the mould of general planar, therefore will not show anti-dazzle Property.In addition, in the case where etch quantity is more than 50 μm, the difference of height for being formed at the concaveconvex shape of metal surface becomes big, using institute The antiglare layer of the Mold Making for obtaining can whiten, therefore not preferred.Etch processes in first etching work procedure both can be utilized 1 time Etch processes carrying out, it is also possible to be divided into 2 times and process be etched with Shangdi.Herein, place is etched being divided into more than 2 times In the case of reason, the total of the etch quantity of the etch processes of more than 2 times is preferably 1～50 μm.
(7) photosensitive resin film stripping process
In ensuing photosensitive resin film stripping process, using in the first etching work procedure as mask use it is remaining Photosensitive resin film fully dissolves removing.In photosensitive resin film stripping process, using stripper photosensitive resin film is dissolved. As stripper, it is possible to use with above-mentioned developer solution identical material, become by making pH, temperature, concentration and dip time etc. Change, the photosensitive resin film of exposure portion is fully dissolved into removing in the case where the photosensitive resin film of minus has been used, The photosensitive resin film of non-exposed portion is fully dissolved into removing in the case of having used the photosensitive resin film of eurymeric.For sense Stripping means in photosensitiveness resin film stripping process using dipping and stripping, spraying it is not also specifically limited, can be peeled off, hairbrush is shelled The method such as peel off from, ultrasound wave.
Figure 10 (b) is schematically shown by photosensitive resin film stripping process, using in the first etching work procedure as mask The photosensitive resin film for using is completely dissolved and the state after removing.By the mask 12 based on photosensitive resin film and etching, First surface concaveconvex shape 15 is formed on the surface of mould base material.
(8) second etching work procedures
In second etching work procedure, by etch processes, make by losing photosensitive resin film as mask is used first The first surface concaveconvex shape 15 carved operation and formed is passivated.By second etch processes, so as to pass through the first etch processes Surface in the first surface concaveconvex shape 15 of formation inclines precipitous partial disappearance, the antiglare layer of the Mold Making obtained by use Optical characteristics to preferable direction change.In Figure 10 (c), the state being shown below：By the second etch processes, so as to mould It is passivated with the first surface concaveconvex shape 15 of base material 7, surface inclines precipitous part and is passivated, is formed and there is gentle surface to incline Oblique second surface concaveconvex shape 16.
The etch processes of the second etching work procedure are also identical with the first etching work procedure, typically by using iron chloride (FeCl3) liquid, copper chloride (CuCl2) liquid, alkali etching liquid (Cu (NH3)4Cl2) etc. corrosion surface carrying out, but can also use The strong acid such as hydrochloric acid, sulphuric acid, the reverse electrolysis etching that can also use by applying the current potential contrary with during plating to carry out.Implement Concavo-convex degree of passivation after etch processes is obtained according to the species of base metal, etching maneuver and using the first etching work procedure Concavo-convex size and depth etc. and it is different, therefore cannot treat different things as the same, but maximum factor in terms of control degree of passivation It is etch quantity.Herein described etch quantity is also identical with the first etching work procedure, is the mould base material being shaved because of etching Thickness.If etch quantity is little, the effect for being passivated the concavo-convex surface configuration obtained using the first etching work procedure is just insufficient, The optical characteristics that the concaveconvex shape is transferred to into antiglare layer obtained by transparent membrane are less good.On the other hand, if etch quantity Excessive, then concaveconvex shape substantially disappears, and becomes the mould of general planar, will not show anti-glare.Thus, etch quantity is preferred In the range of 1～50 μm, in the range of more preferably 4～20 μm.For the etch processes in the second etching work procedure, also with One etching work procedure is identical, both can be carried out by the etch processes of 1 time, it is also possible to be divided into more than 2 times to enter by etch processes OK.Herein, being divided into etch processes more than 2 times come in the case of carrying out, the conjunction of the etch quantity in the etch processes of more than 2 times Meter is preferably 1～50 μm.
(9) second plating operations
Next, by implementing chromium plating, and second surface concaveconvex shape 16 is passivated, and protect die surface.Figure 10 In (d), shape on the second surface concaveconvex shape 16 formed in the etch processes as described above by the second etching work procedure is shown Into chrome plating 17 and make the state that the surface 18 of chrome plating is passivated.
In the present invention, on the surface of flat board or roller etc., using having, gloss, hardness are high, coefficient of friction is little, it is good to give The chromium plating of good release property.The species of chromium plating is not particularly limited, but preferably uses and be referred to as so-called gloss chromium plating or dress Decorations chromium plating etc., show the chromium plating of good gloss.Chromium plating is typically carried out using electrolysis, as its plating bath, using containing There is chromic anhydride (CrO3) and a small amount of sulfur aqueous acid.By adjusting electric current density and electrolysis time, chromium plating can be controlled Thickness.
It should be noted that in the second plating operation, the plating not being preferable to carry out beyond chromium plating.Its reason is, For the plating beyond chromium, hardness, wear resistance meeting step-down, therefore reduce as the durability for mould, using In concavo-convex wear down or mould can occur damage.Using the antiglare layer of this kind of Mold Making, it is difficult to obtain enough anti-dazzle functions Probability is high, in addition, the probability that defect is produced in antiglare layer is also uprised.
In addition, preferably not grinding the surface after plating in the present invention yet.This is based on such as inferior reason, i.e. by grinding Mill and produce flat part in most surface, it is therefore possible to cause the deterioration of optical characteristics, further, since the control of shape because Element increases, therefore, it is difficult to realizing the good shape control of repeatability.
Like this in the present invention, after chromium plating is implemented, preferred not lapped face, but directly using chromium plating face as mould Male and fomale(M＆F) use.Its reason is to implement chromium plating by the surface to being formed with fine surface unevenness profile, it is possible to obtain It is passivated concaveconvex shape and improves the mould of its case hardness.Concavo-convex degree of passivation now is according to base metal Species or thickness of species, the concavo-convex size obtained using the first etching work procedure and depth and plating etc. and it is different, therefore Cannot treat different things as the same, but maximum factor in terms of control degree of passivation remains plating thickness.If the thickness of thin of chromium plating, Then make the effect of the concavo-convex surface configuration passivation of gained before chromium plating processing insufficient, transfer antiglare layer obtained by the concaveconvex shape Optical characteristics it is not so good.On the other hand, if plating thickness is blocked up, not only productivity is deteriorated, but also can produce and claimed Make the plating defect of the overshooting shape of tuberosity, thus it is not preferred.Thus, the thickness of chromium plating is preferably in the range of 1～10 μm, more In the range of preferably 3～6 μm.
The chrome plating formed in the second plating operation is preferably formed in the way of making Vickers hardness reach more than 800, more It is preferred that being formed in the way of reaching more than 1000.In the case where the Vickers hardness of chrome plating is less than 800, when not only mould is used Durability reduce, and hardness reduces because of chromium plating, and its reason is, plating bath composition, electrolytic condition etc. when plating is processed Produce abnormal probability high, cause the probability of undesirable impact also high the generation situation of defect.
＜ protecting film ＞
For the present invention anti-dazzling polarizing plate for, from from the viewpoint of mechanical strength, it is also possible to polarizing coating with It is formed with the contrary side laminating protecting film in antiglare layer side.Protecting film can also be the one-piece type optical compensation films of protecting film. Protecting film as used herein, specifically, preferably uses now most widely used as the protecting film of polarization plates The thin film of the transparent resins such as triacetyl cellulose.
As the example of protecting film used in the present invention, triacetyl cellulose, amorphous polyolefins system tree can be enumerated Membrane of lipoprotein, polyester based resin thin film, acrylic resin thin film, polycarbonate-based resin thin film, polysulfones based resin film, alicyclic ring Formula polyimides system resins thin film etc..In the middle of them, particularly preferably using by triacetyl cellulose or amorphous polyolefins system tree The thin film that fat is constituted.The amorphous polyolefins system resin typically ring with norborene or multi-ring norborneol alkene monomer etc The resin, or cyclic olefin of the polymerized unit of shape alkene and the copolymer of chain olefin.Wherein, thermoplasticity saturation drop ice Piece alkene system resin is representational resin.In addition, the resin for having imported polar group is also effective.As commercially available amorphous polyolefins It is resin, ARTON (JSR (strain) systems), ZEONOR (Japanese ZEON (strain) system), ZEONEX (Japanese ZEON (strain) can be enumerated System), APO (Mitsui Chemicals (strain) system), APEL (Mitsui Chemicals (strain) system) etc..In the amorphous polyolefins using this kind of commercially available product In the case of being resin, the amorphous polyolefins system resin masking is formed into thin film, in masking, can be suitably used molten Method known to agent the tape casting, extrusion by melting etc..
In the case of the side laminating protecting film contrary with antiglare layer side is formed with of polarizing coating, it is also possible to using upper The adhesive stated is fitted.
Saponification process, sided corona treatment, silane coupling agent can also be implemented to binding face before protecting film is fitted in into polarizing coating Process, anchor the easily bonding process such as coating process.
＜ optical compensation films, optical compensating layer ＞
The anti-dazzling polarizing plate of the present invention can also have in the side contrary with antiglare layer side is formed with of polarizing coating Optical compensating layer.The optical compensating layer can be enumerated for the purpose of compensation of phase contrast etc.：Oriented film by various plastics etc. The birefringent film of composition, orientation be fixed with dish-like liquid crystal or nematic liquid crystal thin film, be formed with film substrate it is above-mentioned The optical compensating layer of liquid crystal layer etc..These optical compensating layers both can be only one layer, or multilamellar.Multilamellar is being set In the case of optical compensating layer, optical compensating layer of the same race can be both laminated, it is also possible to stacking optical compensating layer not of the same race.Example Such as, both can be on the one-piece type optical compensation films of protecting film, further by binding agent being laminated by the stretching of various plastics Birefringent film of the compositions such as thin film etc., it is also possible to solidify liquid crystal aligning on the one-piece type optical compensation films of protecting film.
As the plastics for forming birefringent film, for example, can enumerate Merlon, polyvinyl alcohol, polystyrene, poly- Methyl methacrylate, the polyolefin of polypropylene, polyacrylate, polyamide, amorphous polyolefins system resin etc..Stretching Thin film can also be the Jing thin film that uniaxially or biaxially etc. suitable mode has been processed.Alternatively, it is also possible to be, thin with heat-shrinkable Apply contractility and/or tensile force under the bonding of film so as to the birefringence for controlling the refractive index of the thickness direction of thin film is thin Film.
The optical compensating layer formed in the side contrary with antiglare layer side is formed with of polarizing coating can also be in use The adhesive stated and it is integrated, simplicity from bonding operation, prevent the viewpoints such as the generation of optical strain from considering, it is also possible to use Binding agent (also referred to as pressure-sensitive adhesive) described later.
As long as optical compensation films and optical compensating layer are matchingly suitably selected with each drive pattern of liquid crystal cell.As The drive pattern of liquid crystal, can enumerate vertical orientated (Vertical Alignment：VA) pattern, transverse electric field (In-Plane Switching：IPS) pattern, twisted nematic (Twisted Nematic：TN) pattern etc..If vertical alignment mode Liquid crystal cell, then can use by the cellulose-based resin with acylated celluloses such as triacetyl celluloses as representative, cyclic olefin It is that the thin film that the transparent resins with positive refractive anisotrop such as resin, Merlon are constituted enters under suitable condition Gone uniaxially or biaxially stretching with nx＞ ny≥nzRelation thin film.Herein, nxRepresent slow axis side in the face of thin film To refractive index, nyRepresent the refractive index of quick shaft direction in the face of thin film, nzRepresent the refractive index of the thickness direction of thin film.In addition, Annular ethylene series resin is the resin with the cyclic olefin of norborene, dimethano octahydro naphthalene etc as monomer, as commercially available product, There are ARTON (JSR (strain) systems), ZEONOR (Japanese ZEON (strain) system), ZEONEX (Japanese ZEON (strain) system) etc..These transparencys In resin, uneven generation of the face internal characteristic caused by thermal strain from photoelastic coefficient is little, under use condition etc. is few to be considered, suitably Using triacetyl cellulose, annular ethylene series resin.Alternatively, it is also possible to coating, cholesterol using dish-like liquid crystal on substrate The coating on substrate under the short pitch of liquid crystal, the layer for making the inorganic layered compounds such as Muscovitum formed on substrate, resin Gradually or the relation with nx ≈ ny ＞ nz such as simultaneously biaxial drawing, non-stretched solvent cast film optical compensating layer.
In addition, if be the liquid crystal cell of TN patterns, then thin film for obtaining as follows etc. is preferably used：By organic compound, especially Although its be show liquid crystal liquid crystal property and the compound with discoid molecular structure or do not show liquid crystal liquid crystal property however can be because Electric field or magnetic field and show that the compound of negative refractive anisotrop is coated on be made up of triacetyl cellulose etc. transparent On resin film, with make optic axises relative to film normal direction the inclined mode between 5～50 ° be orientated obtained by thin film. Orientation not only can be single direction, for example, can also be to become big so-called mixed successively from the one of thin film facing to another side slope Conjunction to.As the organic compound with discoid molecular structure for showing liquid crystal liquid crystal property, can exemplify low molecule or High molecular dish-like liquid crystal, for example, is combined on the parent nucleus with planar structure such as benzophenanthrene, three polyindenes, benzene with radial It is organic obtained by the substituent groups of straight-chain such as alkyl, alkoxyl, alkyl substituted benzene formyloxy, alkoxy substituted formyloxy Compound.Wherein, preferably the organic compound of absorption is not shown in visible region.These have discoid molecular structure Organic compound not only can be used alone a kind, it is also possible to the orientation required in order to obtain the present invention, and as needed will be several Plant and be used in mixed way, or be used in mixed way with other organic compound such as polymer matrix.As what is be used in mixed way as described above Organic compound, as long as there is intermiscibility with the organic compound with discoid molecular structure, or can be by with circle The organic compound of the molecular structure of plate-like so that the organic compound of the particle size dispersion of the degree of light scattering will not be made, just without spy Do not limit.As be provided with the transparent base film being made up of cellulose-based resin be made up of the liquid crystal compounds layer, Optic axises for example, can suitably use WV thin film (Fuji Photo Film (Ltd.)) relative to the inclined thin film of film normal.Separately Outward, it is also preferred that using the thin film for obtaining as follows：By the organic compound with elongated club shaped structure, especially show nematic Although liquid crystal liquid crystal property and with the compound for providing positive optically anisotropic molecular structure or do not show liquid crystal liquid crystal property however can be because Electric field or magnetic field and show the compound of positive refractive anisotrop, in the transparent base being made up of cellulose-based resin etc. Masking on thin film, with make optic axises relative to film normal direction the inclined mode between 5～50 ° be orientated obtained by thin film. The orientation not only can be single direction, for example, it is also possible to be to become big institute successively facing to another side slope from the one of thin film Meaning hybrid orientation.As the layer, the optic axises that are made up of nematic liquid crystal compound are provided with transparent base film relative to thin film The thin film of normal slope, for example, can suitably use NH thin film (Nippon Oil(Nippon Mitsubishi Oil) (strain) system).
＜ adhesive phase ＞
In for the binding agent that the anti-dazzling polarizing plate of the present invention is fitted with image display device, it is possible to use with third The binding agent of polymer based on olefin(e) acid based polymer, silicone-based polymer, polyester, polyurethane, polyethers etc..Wherein preferably select Following binding agent is using, i.e. as acrylic adhesive, the optical transparency is excellent, keeps the wellability of appropriateness Or cohesiveness, it is also excellent with the cementability of base material, and with weatherability, thermostability etc., under conditions of heating or humidification not The binding agent of the stripping problem such as tilting or stripping can be produced.In acrylic adhesive, following acrylic acid series copolymer is made Based on polymer be useful, i.e. by (methyl) propylene with the alkyl that the carbon numbers such as methyl, ethyl, butyl are less than 20 The Arrcostab and the acrylic acid seriess list containing functional group comprising (methyl) acrylic acid, (methyl) Hydroxyethyl Acrylate etc. of acid Body coordinated in the way of making glass transition temperature be preferably less than 25 DEG C, more preferably less than 0 DEG C obtained by weight average molecular weight For more than 100,000 acrylic acid series polymeric compounds.
For formation of the adhesive phase in polarization plates, for example, can be carried out as follows：It is organic molten in toluene, ethyl acetate etc. Dissolving or dispersible adhesive compositions in matchmaker and prepare the solution of 10～40 weight %, using being coated directly onto in polarization plates And the mode of adhesive phase is formed, or, form adhesive phase on protecting film in advance, by being transferred in polarization plates Form mode of adhesive phase etc. to carry out.The thickness of adhesive phase determines according to its bonding force etc., suitable scope is 1～ 25 μm or so of scope.
＜ image display device ＞
The present invention also provides a kind of image display device, and it possesses above-mentioned anti-dazzling polarizing plate of the invention and image is aobvious Show element, the anti-dazzling polarizing plate is configured at the visible side of image-displaying member with its hard conating side as outside.
Herein, the representational example of image-displaying member is liquid crystal panel, and liquid crystal panel possesses the envelope between upper and lower base plate The liquid crystal cell of liquid crystal is entered, has been applied using voltage and make the state of orientation of liquid crystal change to carry out the display of image.The present invention's In image display device, anti-dazzling polarizing plate is configured in the visible side of image-displaying member.Now, the male and fomale(M＆F) quilt of antiglare layer It is configured to outside (visible side).Like this, the image display device for possessing anti-dazzling polarizing plate of the invention can utilize anti-dazzle The surface that layer has it is concavo-convex make scatter incident light and subtract it is light mirror picture, give excellent visuality.
Embodiment
Embodiment will below be enumerated, and the present invention will be described in more detail, but the present invention is not limited to these enforcements Example.
The ＞ of ＜ embodiments 1
(A) making of polarizing coating
By the thick 75 μm, degree of polymerization 2400, polyvinyl alcohol film single shaft drawing in the way of dry type of saponification degree more than 99.9% 5 times of stretching ratio is extended, while tense situation is kept, respectively containing the iodine of 0.05 weight portion in every 100 weight portion water And 5 weight portion potassium iodide aqueous solution in, impregnate 60 seconds at 28 DEG C of temperature.Then, the state of tense situation is being remained Under, in the boric acid aqueous solution of the potassium iodide of boric acid and 6 weight portions in every 100 weight portion water respectively containing 7.5 weight portions, Impregnate 300 seconds at 73 DEG C of temperature.Thereafter, 10 seconds are cleaned with 15 DEG C of pure water.Thin film after by washing remains tense situation In the state of, it is dried 300 seconds at 70 DEG C, obtain polarizing coating.The thickness of the polarizing coating is 23 μm.
(B) making of micro concavo-convex shape die for forming
The surface for having prepared the aluminum roller to diameter 200mm (A5056 based on JIS) implements the copper-plated instruments of Ba Lade. Silvering/surface copper coating of the Ba Lade copper facing comprising copper coating/thin, the thickness setting of whole coating is for about 200 μm.To the plating Copper surface carries out mirror ultrafinish, in the copper coatings photosensitive resin coating being ground, is dried and forms photonasty tree Adipose membrane.Then, the pattern arranged repeatedly shown in Figure 11 (is run through removing spy from the pattern with random Luminance Distribution The band filter of the composition of fixed spatial frequency range and make) obtained by pattern entered by laser on photosensitive resin film Row exposure, development.Enter by the exposed and developed use Laser Stream FX ((strain) Think Laboratory systems) of laser OK.The photoresist of eurymeric used in photosensitive resin film.
Thereafter, the first etch processes have been carried out with copper chloride liquid.Etch quantity now is set as 4.5 μm.From the first etching Photosensitive resin film is removed on roller after process, the second etch processes is carried out with copper chloride liquid again.Etch quantity setting now For 12 μm.Thereafter, chromium plating processing is carried out, produces mould A.Now, chromium plating thickness is set as 4 μm.
It should be noted that Figure 11 is the figure of a part for the view data for being denoted as the pattern used by the present embodiment. The view data as pattern shown in Figure 11 is the size of 33mm × 33mm, is made with 12800dpi.
Figure 12 is to represent to carry out the pattern shown in Figure 11 power spectrum G obtained by discrete Fourier transform (DFT)2The figure of (f).Root Understand according to Figure 12：Using the One-dimensional power spectrum of the pattern used in the making of antiglare film A (embodiment 1) as relative to space frequency The chart when intensity of rate is represented, in 0.007 μm of spatial frequency- 10.015 μm of the above- 1Hereinafter there is the first maximum, in space 0.05 μm of frequency- 10.1 μm of the above- 1Hereinafter there is the second maximum.
(C) formation of antiglare film
Following each composition is dissolved in ethyl acetate with weight % of solid component concentration 60, is shown after solidification The ultra-violet solidified resin composition A of 1.53 refractive index.
The weight portion of pentaerythritol triacrylate 60
The weight portion of polyfunctional carbamate acrylate 40
(reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate)
Diphenyl (2,4, the 6- trimethoxybenzoy) weight portion of phosphine oxide 5.
By ultra-violet solidified resin composition A to make dried coating thickness be to be coated on thick 40 μ in the way of 7 μm On triacetyl cellulose (TAC) thin film of m, it is dried 3 minutes in 60 DEG C of drying machine is set as.So that light-cured resin group Compound layer is the mode of die side, dried thin film rubber rollers is pushed on the male and fomale(M＆F) of the mould A of previous gained and is made It is closely sealed.It is calculated as 200mJ/cm according to h lines conversion light quantity from TAC film side in this condition2Mode irradiate and carry out self-strength 20mW/cm2High voltage mercury lamp light, make Photocurable resin composition layer solidify.Thereafter, by TAC film and solidified resin one Rise from mould and peel off, produce and had that irregular solidified resin is constituted with the duplexer of TAC film, transparent anti-dazzle by surface Film A.
(D) making of anti-dazzling polarizing plate
Relative to the weight portion of water 100, the carboxy-modified polyvinyl alcohol " Kuraray sold by (strain) Kuraray is dissolved POVAL KL318 " (modified degree 2 moles of %) 1.8 weight portions, then be added thereto to as water soluble polyamide epoxy resin by Firmly 1.5 weight portions are simultaneously for " Sumirez Resin 650 " (aqueous solution of weight % of solid constituent 30) of change Chemtex (strain) sale Dissolving, produces polyethenol series adhesive.
After the side contrary with antiglare layer side is formed with to antiglare film A carries out saponification process, with 10 μm of bar coaters The polyethenol series adhesive that coating is prepared as described above, the polarizing coating for previously having obtained of fitting thereon.Thereafter, it is dry at 80 DEG C Dry 5 minutes, then conserve 1 day in room temperature.Thereafter, the side transfer contrary with antiglare film side is fitted with polarizing coating is formed at The acrylic adhesive layer of 15 μm of the thickness on protecting film, is consequently formed adhesive phase, obtains anti-dazzling polarizing plate A.This is anti-dazzle Property polarization plates A gross thickness be 85 μm.
(E) making of liquid crystal indicator
From the commercially available notebook personal computer of the liquid crystal display cells (i.e. image-displaying member) for being equipped with IPS patterns (visible side) peels off polarization plates before the liquid crystal cell of (VAIO SVS15119FJBS, Sony (strain) make), before liquid crystal cell Face, is fitted above-mentioned in the mode for making the absorption axiss of polarization plates consistent with the absorption direction of principal axis of the polarization plates for being pasted on liquid crystal cell originally Anti-dazzling polarizing plate A, produces liquid crystal panel.Then, the liquid crystal panel is put back to into liquid crystal display cells, produces liquid crystal display Device A (i.e. image display device).
The ＞ of ＜ embodiments 2
Except the thickness of adhesive phase is set in addition to 25 μm, produce same as Example 1ly anti-dazzling polarizing plate B and Liquid crystal indicator B.The gross thickness of anti-dazzling polarizing plate B is 95 μm.
The ＞ of ＜ comparative examples 1
In addition to using thick 60 μm TAC film, antiglare film C is produced same as Example 1ly.In addition, except making Beyond with antiglare film C, anti-dazzling polarizing plate C and liquid crystal indicator C is produced same as Example 1ly.Anti-dazzling polarizing plate C Gross thickness be 105 μm.
The ＞ of ＜ comparative examples 2
Mirror ultrafinish is carried out to the surface of the aluminum roller (A5056 based on JIS) of diameter 300mm, to the aluminum face being ground Using abrasive blasting device ((strain) only making is made), with abrasive blasting pressure 0.1MPa (gauge pressure, same as below), pearl usage amount 8g/ cm2(per 1cm2It is the usage amount of the surface area of roller, same as below) injection Zirconia beads TZ-SX-17 is (Tosoh (strain) systems, flat Equal particle diameter：20 μm), produce surface concavo-convex.Electroless nickel plating processing is carried out to the irregular aluminum roller of band of gained, depanning is made Tool B.Now, electroless nickel plating thickness is set as into 15 μm.In addition to the mould B obtained by use, make same as Example 1ly Make antiglare film D.In addition, in addition to using antiglare film D, anti-dazzling polarizing plate D and liquid crystal are produced same as Example 1ly Display device D.The gross thickness of anti-dazzling polarizing plate D is 85 μm.
The ＞ of ＜ comparative examples 3
The pattern arranged repeatedly shown in Figure 15 (is run through from the pattern with random Luminance Distribution removing specific Spatial frequency range composition band filter and make) obtained by pattern carried out by laser on photosensitive resin film Exposure, by the etch quantity in the first etch processes 4 μm are set as, the etch quantity in the second etch processes is set as into 11 μm, are removed Beyond this, mould C is made same as Example 1ly, in addition to using mould C, antiglare film E is made same as Example 1ly, In addition to using antiglare film E, anti-dazzling polarizing plate E and liquid crystal indicator E is produced same as Example 1ly.Anti-glare The thickness of polarization plates E is 85 μm.
[evaluation of anti-dazzling polarizing plate]
Anti-dazzling polarizing plate to obtaining in above-described embodiment and comparative example has carried out following evaluation.By evaluation result table It is shown in Table 1.In addition, in Figure 13, Figure 14 and Figure 16, illustrating by the anti-glare made in embodiment 1,2 and comparative example 1～3 The common logarithm logH of the One-dimensional power spectrum that the absolute altitude of polarization plates A～E is calculated2(f)。
(1) measure of the surface configuration of anti-dazzling polarizing plate
(measure of the absolute altitude on surface)
Using three-dimensional microscope PL μ 2300 (Sensofar company systems), the absolute altitude on the surface of anti-dazzling polarizing plate is determined. In order to prevent the warpage of sample, make male and fomale(M＆F) using optically transparent binding agent and paste for mode and the glass substrate on surface Close, be subsequently used for determining.During measure, the multiplying power of object lens is set to into 10 times and is measured.Horizontal resolution Δ x and Δ y are 1.66 μm, measure area is 950 μm of 1270 μ m.
(power spectrum of the absolute altitude of fine concave-convex surface)
512 × 512 are sampled from the central part of determination data obtained above (be calculated as 850 μ ms 850 to determine area μm) data, the absolute altitude on the micro concavo-convex surface of anti-dazzling polarizing plate is obtained as two-dimensional function h (x, y).To two-dimensional function h (x, y) carries out discrete Fourier transform (DFT) and obtains two-dimensional function H (fx, fy).Two-dimensional function H (fx, fy) square is calculated two The two-dimensional function H of dimension power spectrum2(fx, fy), calculates the one-dimensional functions H away from the function apart from f of origin, i.e. One-dimensional power spectrum2 (f).The absolute altitude on the surface at 5 positions is determined to each sample, the one-dimensional functions H that the One-dimensional power calculated by these data is composed2 F one-dimensional functions H that the meansigma methodss of () are composed as the One-dimensional power of each sample2(f)。
(2) measure of the optical characteristics of anti-dazzling polarizing plate
(mist degree)
Total mist degree of anti-dazzling polarizing plate is determined as follows：By anti-dazzling polarizing plate with optically transparent binding agent with it is anti- Dizzy layer forms the face of face opposite side and fits with glass substrate, the anti-dazzling polarizing plate to fitting in the glass substrate, from glass Substrate-side incident light, using haze meter " HM-150 " type according to color technical research institute in (strain) village of JIS K 7136 Determine.
(transmission vividness (original text：Fresh lightness))
Using the image definition determinator " ICM-1DP " of SUGA testing machines (strain) system according to JIS K 7105, determine Go out the transmission vividness of anti-dazzling polarizing plate.In this case, also for the warpage for preventing sample, glued using optically transparent Mixture is fitted in the way of making the fine concaveconvex shape face of antiglare layer as surface with glass substrate, is subsequently used for determining.At this From glass side incident light under state, it is determined.Measured value herein is respectively using the width of dark portion and highlights The aggregate value of the value that 4 kinds of light combs of 0.125mm, 0.5mm, 1.0mm and 2.0mm are determined.In this case transmission vividness is most Big value is 400%.
(reflection vividness)
Using the image definition determinator " ICM-1DP " of SUGA testing machines (strain) system according to JIS K 7105, determine Go out the reflection vividness of anti-dazzling polarizing plate.In this case, also for the warpage for preventing sample, glued using optically transparent Mixture in the way of making the fine concaveconvex shape face of antiglare layer as surface with black acrylic baseplate-laminating, be subsequently used for surveying It is fixed.It is determined with 45 ° of incident light from concaveconvex shape surface side in this condition.Measured value herein is to use dark portion and bright The width in portion is respectively the aggregate value of the value that 4 kinds of light combs of 0.5mm, 1.0mm and 2.0mm are determined.In this case reflection is distinct The maximum of degree is 300%.
(3) evaluation of anti-dazzling polarizing plate
The liquid crystal indicator made in above (visible side) additional anti-dazzling polarizing plate is set in bright room Black dispaly state, visually observes and mirrors state, whiting.Then, white dispaly state is set in bright room, to dazzling also to enter Visual observation is gone.It is as follows for the metewand for mirroring state, whiting, dazzle.
(mirroring)
1：Do not observe and mirror.
2：Slightly it was observed that mirroring.
3：It is clearly observed and mirrors.
(whiting)
1：Whiting is not observed.
2：Slightly it was observed that whiting.
3：It is clearly observed whiting.
(twinkling)
1：Can't see twinkling.
2：Atomic observing less is dazzled.
3：Significantly it was observed that dazzling.
[table 1]
As shown in table 1, for anti-dazzling polarizing plate A～C (embodiment 1 and 2, comparative example 1), the power spectrum of absolute altitude it is conventional Second dervative d with regard to spatial frequency of logarithm2logH2(f)/df2In 0.01 μm of spatial frequency- 1Place is less than 0, in spatial frequency 0.02μm- 1Place is more than 0.Thus, as shown in FIG. 13 and 14, by the conventional of the power spectrum of the absolute altitude of anti-dazzling polarizing plate A～C The chart that logarithm is represented as the intensity relative to spatial frequency, in 0.01 μm of spatial frequency- 1Place has convex shape, In 0.02 μm of spatial frequency- 1Place has shape convex downwards.
On the other hand, for anti-dazzling polarizing plate D (comparative example 2), the common logarithm of the power spectrum of absolute altitude with regard to space Second dervative d of frequency2logH2(f)/df2In 0.01 μm of spatial frequency- 1Place is more than 0, in 0.02 μm of spatial frequency- 1Place is less than 0.As a result, as shown in figure 14, using the common logarithm of the power spectrum of anti-dazzling polarizing plate D as relative to the strong of spatial frequency The chart that degree is represented, in 0.01 μm of spatial frequency- 1Place has shape convex downwards, in 0.02 μm of spatial frequency- 1Place has upwards Convex shape.
In addition, for anti-dazzling polarizing plate E (comparative example 3), the common logarithm of the power spectrum of absolute altitude with regard to spatial frequency Second dervative d2logH2(f)/df2In 0.01 μm of spatial frequency- 1Place is more than 0, in 0.02 μm of spatial frequency- 1Place is also greater than 0. As a result, as shown in figure 16, using the common logarithm of the power spectrum of anti-dazzling polarizing plate E as the intensity relative to spatial frequency The chart of expression, in 0.01 μm of spatial frequency- 1Place has shape convex downwards, in 0.02 μm of spatial frequency- 1Place also has downward Convex shape.
The anti-dazzling polarizing plate A and B (embodiment 1 and 2) of important document of the present invention are met despite low haze, but still be able to show Required enough anti-glares and excellent twinkling inhibition are shown.On the other hand, show and anti-dazzling polarizing plate A and B The anti-dazzling polarizing plate C (comparative example 1) of identical spatial frequency characteristic although also showing that required enough anti-glares, but Because the thickness of polarization plates is 105 μm, therefore it is observed that twinkling.In addition, using the common logarithm of the power spectrum of absolute altitude as The chart represented relative to the intensity of spatial frequency is in 0.02 μm of spatial frequency- 1Anti-glare of the place with convex shape is inclined Vibration plate D (comparative example 2) can consumingly be observed and dazzled.In addition, using the common logarithm of the power spectrum of absolute altitude as relative to sky Between frequency the chart that represents of intensity in 0.01 μm of spatial frequency- 1Place has the anti-dazzling polarizing plate E (ratios of shape convex downwards Compared with example 3) generate and mirror, anti-glare is insufficient.
The explanation of symbol
1 anti-dazzling polarizing plate, 101 polarizing coatings, 102 antiglare layers, 103 imaginary planes, 2 fine concavo-convex, 3 throwings Shadow face, 5 principal normal directions, the normal of 6 local, the normal vector of 6a～6d polygon facets, 7 mould base materials, 8 pass through to grind The surface of the mould base material that grinder sequence has been ground, 9 photosensitive resin films, 10 regions being exposed, 11 areas not being exposed Domain, 12 masks, 13 regions without mask, 15 first surface concaveconvex shapes (the base material table of the mould after the first etching work procedure The concaveconvex shape in face), 16 second surface concaveconvex shapes (concaveconvex shape of the mould substrate surface after the second etching work procedure), The surface of 17 chrome platings, 18 chrome platings.

Claims (4)

1. a kind of anti-dazzling polarizing plate, it is characterised in that be comprising the polarizing coating being made up of polyvinyl alcohol resin and be formed at Antiglare layer on the polarizing coating, total mist degree is less than 1%, and thickness is less than 100 μm of anti-dazzling polarizing plate,
The antiglare layer possesses with fine concavo-convex micro concavo-convex surface in the side contrary with the polarizing coating,
The One-dimensional power spectrum H of the absolute altitude on the micro concavo-convex surface2The second dervative with regard to spatial frequency f of the common logarithm of (f) d2logH2(f)/df2In 0.01 μm of spatial frequency- 1Place is less than 0, in 0.02 μm of spatial frequency- 1Place is more than 0.
2. anti-dazzling polarizing plate according to claim 1, wherein,
In the micro concavo-convex surface, angle of inclination is that the ratio in more than 5 ° of small face is less than 1%.
3. anti-dazzling polarizing plate according to claim 1 and 2, wherein,
The maximum cross-section height Rt on the micro concavo-convex surface is less than more than 0.3 μm 1 μm.
4. a kind of image display device, it is characterised in that
Any one of claims 1 to 3 institute is configured with the opposite side on the micro concavo-convex surface and the opposite mode of liquid crystal cell The anti-dazzling polarizing plate stated.
CN201380066524.4A 2012-12-18 2013-11-20 Antiglare polarizing plate and image display device Expired - Fee Related CN104871050B (en)

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