CN103649793B - Polarization element and polarizer - Google Patents

Polarization element and polarizer Download PDF

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Publication number
CN103649793B
CN103649793B CN201280035152.4A CN201280035152A CN103649793B CN 103649793 B CN103649793 B CN 103649793B CN 201280035152 A CN201280035152 A CN 201280035152A CN 103649793 B CN103649793 B CN 103649793B
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wavelength region
polarizer
polarization element
film
dichroic dye
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CN103649793A (en
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矢作悦幸
田中兴
田中兴一
樱井弘
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/113—Fluorescence

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention relates to a kind of polarizer, it is suitable for being output as 440nm~470nm blue led or blue-fluorescence pipe as the fluorescence excitation color crossover display terminal of light source so that maximum is luminous, the polarizer is characterised by, its contrast is high and transmitance of when light leak is few, light is passed through is high.Polarization element and polarizer involved in the present invention be characterised by, Tp >=30% in 440nm≤λ≤470nm wavelength region, and CR >=8 in the wavelength region between any continuous 20nm, 000, CR >=5,000 in remaining wavelength region, and at least contain dichroism pigment.

Description

Polarization element and polarizer
Technical field
The present invention relates to polarization element and use its polarizer.
Background technology
Polarization element typically by make as dichroism pigment iodo-complexes or dichroic dye adsorb in polyethylene On alcohol resin film and it is orientated and is manufactured.The diaphragm being made up of triacetyl cellulose etc. is fitted across cement layers In at least one side of the polarization element, so as to form polarizer.Polarizer has light transmission/shielding function, therefore as tool There are the basic constituent components of the display devices such as the liquid crystal and liquid crystal display (LCD) of light switch function.LCD suitable application area Also notebook computer, word processor, liquid crystal projection apparatus, liquid crystal electricity are extended to from small machines such as the calculators and clock and watch at initial stage The broad ranges such as the measurement machine depending on machine, vehicle mounted guidance, mobile phone and indoor and outdoor, and can be in low temperature~high temperature, low humidity ~high humility, low light quantity~high light quantity it is extensive under the conditions of use.It is therefore desirable to which polarizing properties are high and excellent in te pins of durability inclined Shake piece.In addition, the polarizer using iodo-complexes as dichroism pigment is referred to as iodine system polarizer；On the other hand, using two Color dyestuff is referred to as dyestuff system polarizer as the polarizer of dichroism pigment.Among them, from the side that optical characteristics is excellent Face is set out, commonly using iodine system polarizer.For dyestuff system polarizer, if being carried out to the polarizer with identical degree of polarization Compare, then the transmitance of dyestuff system polarizer is less than iodine system polarizer, i.e., it has the problem of contrast is low, but it has height resistance to Feature as hot, high wet heat durability, therefore (patent document 1) is used in color liquid crystal projecting apparatus etc..
Now, the light source in the LCD headed by liquid crystal TV set is the light source using CCFL or high-pressure sodium lamp, further, Such as patent document 2, the light emitting diode (LED) of patent document 3 are popularized in recent years, and White LED is widely used.For making For the polarizer of these light sources, it is used for as known common neutral gray iodine polarizer.Iodine polarizer It is useful for CCFL or high-pressure sodium lamp and White LED etc. with the high feature of the contrast in wider wavelength region 's.
Opened in addition, the effect for the liquid crystal panel being made up of polarizer and liquid crystal is not only through light as light and masking light Function is closed, also having both in liquid crystal panel has colour filter, play the effect of display image.As its research topic, exist just like Under it is described such the problem of：Due to the differently- oriented directivity of liquid crystal, light leak can be occurred according to the difference of the angle of viewing image So that being difficult to see that image, i.e. angle of visibility is narrow.For the species of liquid crystal, can take VA types (vertical orientating type), The various ways such as TN types (twisted nematic), IPS (plane inner switching type), although the degree of its angle of visibility has difference, but No matter there is the problem of angle of visibility is narrow in which kind of mode.In order to make up the narrow of the angle of visibility, TAC (three second are widely used for Acyl cellulose) optical compensation films such as film, wherein, these optical compensation films are by making PC (makrolon) film, COP (cycloolefin) Film, discotic mesogenic are specific direction is orientated and is coated.
As the display for having used liquid crystal technology, in the past since known have following displays (hereinafter referred to as fluorescence excitation Color crossover display terminal), wherein, using such as blue LED as backlight, and possess because blue light is excited And send the fluorophor of a variety of colors light to replace colour filter.For example as disclosed in patent document 4.This fluorophor Excite the liquid crystal display device of color conversion regime to carry out wavelength convert to the light projected by backlight by fluorophor, pass through institute Obtained fluorescence carries out desired color and shown.The liquid crystal display device is different from the liquid crystal display device of colour filter mode, Due in the absence of the optical absorption loss caused by because of colour filter, therefore with the high such feature of light utilization ratio.In addition, its feature Be, in the absence of it is narrow such as the angle of visibility of problem in conventional LCD the problem of, can obtain high image quality image show Show.For such light source, the light source of blue region has been used to improve the luminous efficiency of fluorophor.Blue region Light source use the maximum luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm.
Under normal circumstances, for flat-panel monitor, whole images are in the picture in the range of whole angle of visibilities Contrast is needed for more than 50.It is further preferred that contrast is needed for more than 100 in picture." contrast in picture " refers to The ratio between brightness of brightest pixel and most dark pixel in the state of one image of display.It should be noted that commonly used " face The ratio between brightness when plate contrast " is the brightness and completely black display when showing in vain entirely.But, carry out complete white display or completely black display Such image there's almost no in reality.In addition, the sense of fatigue of eyes can strengthen if contrast is too high.Therefore, as The requirement specification of contrast based on ergonomics, it is more than 50, more preferably more than 100 (non-to recommend " contrast in picture " Patent document 1).
Contrast changes according to the difference for the periphery illumination for watching flat-panel monitor in required picture.That is, Periphery illumination is brighter, then contrast is smaller in required picture；Periphery illumination is darker, then contrast is got in required picture Greatly.When the periphery illumination is changed in the range of 0lux~500lux, the value of contrast is shown in table 1 in required picture.
[table 1]
It is used as the average signal level ASL (Average Signal Level) of common television broadcasting or average bright Spend level ALL (Average Luminance Level) feature, it has been reported that average out to ASL40%, ALL20% or so, model Enclose is ASL20%~60% or so, ALL5%~40% or so.It is reported that：This is watched for 65 inches of television set by size During a little images, in the case where common living environment is illumination 180lux, the height of television set (is set to by H with viewing distance 3H When 3 times of distances) be 240cd/m as the most preferred high-high brightness of television set when watching2(non-patent literature 2).Herein, When common parlor periphery illumination is 180lux, contrast is more than 50 in picture in parlor, is understood according to table 1 in darkroom Contrast is needed for more than 200 in picture.
The condition that contrast becomes minimum in picture is when picture integrally shows dark image.Show most dark image When, it may be said that the brightness of brightest pixel is 5% or so (non-patent literature 3) of high-high brightness in picture.High-high brightness is 240cd/m2Display in the case of, in picture the brightness of brightest pixel be 12cd/m2Left and right.In such a situa-tion, it is It is more than 200, it is necessary to which the brightness of most dark pixel in picture is suppressed in 0.06cd/m to make contrast in picture2Left and right with Under.That is, the brightness in order to meet the brightest pixel in picture is 240cd/m2, most dark pixel in picture brightness be 0.06cd/m2Such above-mentioned condition, panel contrast is needed for 4,000.It should be noted that panel contrast represents to utilize When transmitance when light when a pair of polarizers clip liquid crystal panel is through (parallel Nicolle) is with light shield (cross Nicols) The ratio between transmitance.
The relation of contrast, panel contrast and polarizer contrast in picture in fluorescence excitation color crossover display terminal It is shown in table 2.
[table 2]
CR in picture 50 100 200 250 300 350
High-high brightness [cd/m2] 240 240 240 240 240 240
5% [cd/m of full brightness2] 12 12 12 12 12 12
It is required that black level [cd/m2] 0.240 0.120 0.060 0.048 0.040 0.034
Panel CR 1,000 2,000 4,000 5,000 6,000 7,000
Polarizer CR 2,000 4,000 6,000 8,000 10,000 15,000
It can be seen from table 2：In the case where panel contrast is 4,000, polarizer contrast is needed for 6,000.Need Illustrate, the polarizer contrast in table 2 represents light through the light under state when Nicolle (open mode/polarizer parallel) Energetic transmittance Ep and light shielding state (during closed mode/polarizer cross Nicols) under light energetic transmittance Ec it Than.The energetic transmittance Ep of light represents that light passes through the light that luminescent coating unit area is incided in the provision wavelengths scope under state Light quantity (blue light) energy.The energetic transmittance Ec of light under masked state represents the provision wavelengths model under light shielding state The energy of the light quantity (blue light) of the light of luminescent coating unit area is incided in enclosing.
In the mode of fluorescence excitation color crossover display terminal, R is generated by making blue light incide on fluorophor, G, B white lights, the brightness of display device is to be multiplied by the value of visibility by the light splitting radiance of the light after light-emitting phosphor and determined , but the light splitting radiance of light that autofluorescence body is sent is proportional to the projectile energy of the blue light of excited fluophor, and this is It is well-known.Even in addition, blue light can similarly occur through influence of depolarization caused by liquid crystal panel etc..According to Above-mentioned reason, the polarizer contrast (Ep/Ec) based on the energetic transmittance required for a pair of polarizers are it is considered that with being based on The polarizer contrast (Tp/Tc) of spectrophotometric transmittance is of equal value.It should be noted that Tp refer to by 2 polarization elements according to Spectrophotometric transmittance (transmitance during parallel Nicolle) when the parallel mode of its respective absorption axis is overlapping；Tc refers to 2 Spectrophotometric transmittance (transmitance during cross Nicols) of the polarization element according to the orthogonal mode of its respective absorption axis when overlapping. But, the emission wavelength of fluorophor depends on the band structure shown by fluorescent material, therefore is not to be conceived to specifically The excitating light strength of wavelength, and need the energy for estimating the light of excited fluophor overall.
According to the above, when the polarizer contrast (Ep/Ec) of the energetic transmittance based on light is 6,000, particularly Between the arbitrary wavelength that the maximum of backlight lights in output area, the polarizer contrast (Tp/ based on spectrophotometric transmittance Tc) need to be the numerical value more than 6,000, preferably contrast (Tp/Tc) is 8,000.In addition, in order that the energy based on light is passed through The contrast (Ep/Ec) of rate is higher numerical value, it is also desirable to make the polarizer contrast (Tp/Tc) based on spectrophotometric transmittance for more High numerical value.
It may be said that more preferably under 300lux contrast >=100 in picture.In this case, according to Tables 1 and 2, darkroom Contrast >=350, polarizer contrast >=15,000 based on energetic transmittance in interior picture, as based on spectrophotometric transmittance Polarizer contrast, particularly backlight maximum light output area in arbitrary wavelength between, it is necessary to which contrast is More than 20,000.
In addition, the liquid crystal display device of mode shows the Luminance Distribution of the probably directive property of reflection backlight in the past, and The mode of fluorescence excitation color crossover display terminal is characterised by, utilizes the luminous (Deng Fang development of the isotropism based on fluorophor Light), angle of visibility is wider.On the other hand, then surface brightness is reduced if directive property is low.It may be said that being turned to by 30 degree of changes of full width at half maximum (FWHM) During 45 degree of full width at half maximum (FWHM), front face brightness probably reduces half.
For the image signal of common television set and video, in 0~255 gray scale that can be generally shown with 8bit In, shown using 16~235 gray scales.But, it can be used under the brightness amplification mode for being referred to as ultrawhite pattern to 255 ashes Degree.During complete white display, 400cd/m can be obtained in 235 gray scales2Brightness in the case of, 255 gray scales are shown under ultrawhite pattern When brightness about 1.2 times of 487cd/m can be obtained when being set as γ 2.22.Full white luminance and ultrawhite mould are shown in table 3 The comparison of maximum display brightness under formula.In the mode of fluorescence excitation color crossover display terminal, it is known that the light of polarizer is passed through It is most preferred brightness i.e. 240cd/ when the energetic transmittance Ep of light under state (during parallel Nicolle) value is more than 30% m2.In order to obtain more than Ep30%, transmitance Tp during parallel Nicolle in terms of spectrophotometric transmittance is necessary for more than 30%.
[table 3]
Known common neutral gray iodine polarizer contrast in wider wavelength region is higher, but for fluorescence Excite color crossover display terminal, it is maximum luminous be output as in 440nm~470nm blue-light source region, light leak is more and nothing Method obtains sufficient contrast, and brightness is also not enough.In the polarizer in as fluorescence excitation color crossover display terminal, it is Obtain high-high brightness 240cd/m2And require Ep >=30% and in order to obtain 240cd/m2High-high brightness and more than 200 Picture contrast in darkroom and require polarizer contrast (Ep/Ec) 6,000, so far also can reach it is above-mentioned will The polarizer asked.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-027708
Patent document 2：Japanese Patent No. 3585097
Patent document 3：Japanese Patent No. 4686644
Patent document 4：Japanese Unexamined Patent Publication 2009-134275
Non-patent literature
Non-patent literature 1：SID’03Digest p.779
Non-patent literature 2：Electronic information communication association paper will (Electricity Zi Qing Reported Communications Society Theory texts Chi), J91-A (6), pp.630-638(2008)
Non-patent literature 3：JJAP vol.46,3B,2007,p.1358
The content of the invention
Invent problem to be solved
As described above, as using the maximum luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm as There is contrast with respect to the wavelength in the polarizer of the fluorescence excitation color crossover display terminal of light source, known iodine system polarizer Region is relatively low, can occur light leak or the problem of transmitance when light is passed through is low etc, therefore can not obtain sufficient display figure Picture.Therefore, problem of the invention is to provide a kind of polarization element and polarizer suitable for the display, it is characterised in that should Polarization element and polarizer contrast are high and transmitance of when light leak is few, light is passed through is high.
The means to solve the problem
In order to solve above-mentioned problem, present inventor has performed further investigation, be as a result found that at least containing dichroism pigment, The high polarization element of transmitance when the contrast of 440nm≤λ≤470nm wavelength region is high and light is passed through and polarizer can To solve above-mentioned problem, so as to complete the present invention.
That is, the present invention relates to：
(1) a kind of polarization element, it is used for the maximum luminous blue led or blue-fluorescence for being output as 440nm~470nm The fluorescence excitation color crossover display terminal for light source is managed, the polarization element is characterised by, in 440nm≤λ≤470nm wavelength CR >=8,000 in wavelength region between Tp >=30% in region, and the 20nm of arbitrary continuation in the wavelength region, at remaining Wavelength region in CR >=5,000, and at least contain dichroism pigment.
Herein, λ represents wavelength；Tp refer to by 2 polarization elements according to the parallel mode of its respective absorption axis it is overlapping when Spectrophotometric transmittance (transmitance during parallel Nicolle)；Tc refers to 2 polarization elements are orthogonal according to its respective absorption axis Mode it is overlapping when spectrophotometric transmittance (transmitance during cross Nicols)；CR is the abbreviation of contrast, and it is represented by Tp/Tc The value of composition.
(2) polarization element as described in (1), it is characterised in that in 420nm≤λ ＜ 440nm wavelength region, Tp >= 30% and CR >=1,500.
(3) polarization element as described in (1) or (2), it is characterised in that in 470nm ＜ λ≤490nm wavelength region, Tp >=30% and CR >=1,000.
(4) polarization element as described in any one of (1)~(3), wherein, dichroism pigment at least contains dichroic dye (A) dichroic dye (B) represented by one kind, and/or formula (1) in group.
Dichroic dye (A) group：
C.I. direct orange 26
C.I. direct orange 39
C.I. direct orange 107,
Dichroic dye (B)：
[changing 1]
(in formula, R1、R2Hydrogen atom, low alkyl group, lower alkoxy are represented independently of one another；N represents n=1~3)
(5) polarization element as described in any one of (1)~(4), it is characterised in that in 500nm≤λ≤560nm wavelength In region, transmitance is less than 2%.
(6) polarization element as described in any one of (1)~(3), it is characterised in that dichroism pigment is iodo-complexes, and Tc(λ460)≤Tc(λ600)。
Herein, Tc (λ 460) be by 2 polarization elements according to the orthogonal mode of its respective absorption axis it is overlapping when (orthogonal Buddhist nun During section's ear) the spectrophotometric transmittance at 460nm；Tc (λ 600) is that 2 polarization elements are orthogonal according to its respective absorption axis Mode it is overlapping when the spectrophotometric transmittance at 600nm (during cross Nicols).
(7) polarizer described in any one of (1)~(6), wherein, the polarizer is by least single of polarization element Support film is set on face.
(8) polarizer as described in (7), wherein, at least one side of support film is PET (polyester) film.
(9) a kind of polarizer with inorganic substrate, it is characterised in that (1)~(6) are laminated with inorganic substrate any Polarization element described in or the polarizer described in (7) or (8).
Invention effect
The polarization element of the present invention and had using its polarizer in 440nm≤λ≤470nm wavelength region high partially Optical property, can be provided suitable for using 440nm~470nm blue led or blue-fluorescence pipe as the fluorescence excitation color of light source The polarizer of crossover display terminal.
Brief description of the drawings
Fig. 1 is the Tp of the spectral photometry value for each wavelength that unit distance is 5nm
Fig. 2 is the Tc of the spectral photometry value for each wavelength that unit distance is 5nm
Embodiment
For the polarization element of the present invention, Tp >=30% in 440nm≤λ≤470nm wavelength region, and at this CR >=8,000 in wavelength region in wavelength region between the 20nm of arbitrary continuation, CR >=5,000 in remaining wavelength region.It is logical The polarization element using such present invention is crossed, can be made with the maximum luminous blue led or indigo plant for being output as 440nm~470nm Color fluorescent tube obtains sufficient brightness and contrast for the fluorescence excitation color crossover display terminal of light source.For the aobvious of the display Show, in 440nm≤λ≤470nm wavelength region, CR ＜ 8,000 in the wavelength region between any continuous 20nm, at it Under the conditions of CR ＜ 5,000 are such in commplementary wave length region, it is intended to sufficient contrast can not be obtained, therefore any continuous CR >=8,000 are needed in wavelength region between 20nm, CR >=5,000 are needed in remaining wavelength region.Preferably, exist It is CR >=10,000 in wavelength region in 440nm≤λ≤470nm wavelength region between the 20nm of at least arbitrary continuation, more excellent Select CR >=15,000.It may further be preferable that for 450nm≤λ≤460nm wavelength region, CR >=20,000.On contrast Angle value, CR values can be improved by the veneer transmitance for reducing polarization element, but in this case, Tp values can also reduce and can not Obtain sufficient brightness.Under conditions of Tp ＜ 30%, it is intended to sufficient brightness can not be obtained；Under the conditions of Tp >=30%, light profit It is excellent with efficiency, power consumption can be reduced.It is preferred that Tp >=31%, more preferably Tp >=32%.
Further, for the polarization element of the present invention, preferably in 420nm≤λ ＜ 440nm wavelength region, Tp >=30% and CR >=1,500.The luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm of preferred pair maximum is further The weak light having in short wavelength side is controlled, for the display of the display, the CR ＜ 1,500 in above-mentioned wavelength region Under the conditions of, contrast tends to reduction, preferably CR >=1,500, more preferably CR >=3,000, further preferred CR >=5,000.Separately Outside, the wavelength region with above-mentioned 440nm≤λ≤470nm is same, in the case of Tp ＜ 30%, it is intended to can not obtain sufficiently Brightness；In the case of Tp >=30%, the utilization ratio of light is excellent, can reduce power consumption.It is preferred that Tp >=31%, more preferably Tp >=32%.
Further, for the polarization element of the present invention, preferably in 470nm ＜ λ≤490nm wavelength region, Tp >=30% and CR >=1,000.The luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm of preferred pair maximum is further The weak light having in long wavelength side is controlled, for the display of the display, the CR ＜ 1,000 in above-mentioned wavelength region Under the conditions of contrast tend to reduction；It is preferred that CR >=1,000, more preferably CR >=2,500, further preferred CR >=4,000.Separately Outside, the wavelength region with above-mentioned 440nm≤λ≤470nm is same, in the case of Tp ＜ 30%, it is intended to can not obtain sufficiently Brightness；In the case of Tp >=30%, the utilization ratio of light is excellent, can reduce power consumption.It is preferred that Tp >=31%, more preferably Tp >=32%.
The polarization element of the present invention at least contains dichroism pigment.As dichroism pigment, for example, iodine complexing Thing, dichroic dye etc..
During using dichroic dye as the dichroism pigment of the polarization element for the present invention, dichroism dye is preferably used Dichroic dye (B) represented by least one of material (A) group, and/or formula (1).
Dichroic dye (A) group：
C.I. direct orange 26
C.I. direct orange 39
C.I. direct orange 107
Dichroic dye (B)：
[changing 2]
(in formula, R1、R2Hydrogen atom, low alkyl group, lower alkoxy are represented independently of one another；N represents 1~3)
Dichroic dye (A) group is to show high dichromatic dyestuff, it is characterised in that show maximum contrast angle value Wavelength (λ max) be 420nm≤λ max≤460nm.Wherein, more preferably using C.I. direct oranges 39.
Dichroic dye (B) shown in formula (1) is to show high dichromatic dyestuff, it is characterised in that show maximum The wavelength (λ max) of contrast value is 450nm≤λ max≤470nm.
In formula (1), R1、R2Preferably hydrogen atom.Additionally, it is preferred that be the mixture being made up of the compound of n=1~3, its The ratio of total weight of compound of the weight relative to n=1 and n=3 of the preferred n=2 of ratio compound be more than 55%, More preferably more than 65%, it is more preferably more than 75%, is most preferably more than 85%.
In addition, the dichroic dye (B) shown in formula (1) can be obtained by the method synthesis described in WO2007/138980.
More preferably share at least one of dichroic dye (A) group and dichroic dye (B).Under normal circumstances, compare In the optical characteristics for individually using polarization element obtained from dichroic dye, share different dichroic dyes and obtain Polarization element optical characteristics tend to decline, on the other hand, the present invention in share in dichroic dye (A) group at least one Kind and dichroic dye (B) respective characteristic will not be hindered, result is that λ max characteristic is improved, can in wide band body Reveal high characteristic.Resulting polarization element is characterised by that its λ max is 440nm≤λ max≤470nm；With using two respectively Polarization element obtained from color dyestuff (A) group or dichroic dye (B) compares, and shares different dichroic dyes and obtains Polarization element more high contrast values can be obtained in the case of equal Tp, can be obtained in the case of equal contrast value To higher Tp values.In addition, polarization element obtained from sharing different dichroic dyes can be in broader wavelength region Obtain high contrast values.
When sharing at least one of dichroic dye (A) group and dichroic dye (B), for dichroic dye (A) group It is not particularly limited with the mixing ratio of dichroic dye (B), but is commonly angled relative to dichroic dye (A) and organizes 100 parts by weight, two Color dyestuff (B) is the parts by weight of 25 parts by weight~400；100 parts by weight, dichroism dye are organized preferably with respect to dichroic dye (A) It is the parts by weight of 50 parts by weight~200 to expect (B).
It is not particularly limited, for example, can be enumerated using the manufacture method of the polarization element of these dichroic dyes：Make suction Polyvinyl alcohol mesentery with dichroic dye carries out the film of orientation, dichroic dye is coated on to the base after friction treatment The film or element that are orientated after on material film, dichroic dye is set to mix and be coated on after friction treatment with liquid-crystalline resin The film or element that are orientated after on base material film, make after dichroic dye mixes and be coated on base material film with liquid-crystalline resin By share (sharing) and be orientated film or element, dichroic dye is at least being stretched in single shaft direction The film of dyeing orientation has been carried out on film after orientation, has made the mixed with resin such as dichroic dye and plastics and at least enters in single shaft direction Film that stretching of having gone is orientated etc..The polyvinyl alcohol mesentery for being adsorbed with dichroic dye is preferably set to carry out the film of orientation, its Highest contrast value can be obtained.
The manufacture method of polyvinyl alcohol resin for constituting polarization element is not particularly limited, and can use known Method is manufactured., for example can be by carrying out soap to polyvinyl acetate system resin as the manufacture method of polyvinyl alcohol resin Change and obtain.As polyvinyl acetate system resin, in addition to as the polyvinyl acetate of the homopolymer of vinyl acetate, Can also enumerate vinyl acetate with can be with the copolymer of the other monomers of its copolymerization etc..As with vinyl acetate copolymerization Other monomers, for example, unsaturated carboxylic acid class, olefines, vinyl ethers or unsaturated sulfonic acid class etc..Polyvinyl alcohol Be resin saponification degree be preferably generally 85 moles of %~100 mole %, more preferably 95 moles of more than %.The polyethenol series Resin can be further modified, for example, can use by aldehydes modified polyvinyl formal or Pioloform, polyvinyl acetal Deng.In addition, the degree of polymerization of polyvinyl alcohol resin is preferably generally 1,000~10,000, more preferably 1,500~7,000.
The film that the polyvinyl alcohol resin is filmed is used as base film (former anti-Off ィ Le system).For polyethylene The film-forming method of alcohol system resin is not particularly limited, and known method can be used to be filmed.In this case, polyvinyl alcohol Resin film can be used as plasticizer containing glycerine, ethylene glycol, propane diols or low molecular poly etc..It is plasticized dosage preferred For the weight % of the weight % of 5 weight %~20, more preferably 8 weight %~15.For the base film being made up of polyvinyl alcohol resin Thickness be not particularly limited, such as preferably 5 μm~150 μm, more preferably 10 μm~100 μm.
Implement to be swelled process first for above-mentioned polyvinyl alcohol resin film.It is by making polyethenol series tree to be swelled process Adipose membrane impregnates 30 seconds~10 minutes to carry out in 20 DEG C~50 DEG C of solution.Solvent is preferably water.Polarisation is manufactured shortening In the case of the time of element, it can be also swelled in the dyeing processing of pigment, therefore can also omit and be swelled process.
After process is swelled, implement dyeing process.Dyeing process be by by polyvinyl alcohol resin film immersion containing Have in the solution of dichroic dye to carry out.Solution temperature in the process is preferably 5 DEG C~60 DEG C, more preferably 20 DEG C~ 50 DEG C, particularly preferably 35 DEG C~50 DEG C.The time of dipping in the solution can suitably be adjusted, preferably according to 30 seconds~20 minutes It is adjusted, is more preferably 1 minute~10 minutes.For colouring method, preferably it is immersed in the solution, can also be by should Solution coating on polyvinyl alcohol resin film in carrying out.
Solution containing dichroic dye can contain the conducts such as sodium chloride, sodium sulphate, anhydrous sodium sulfate, sodium tripolyphosphate Dyeing assistant.Their content can be adjusted to arbitrary concentration according to the chromatic time based on dyestuff, temperature, as Their own content is preferably 0~5 weight %, more preferably the weight % of 0.1 weight %~2.
After dyeing process, into matting (hereinafter referred to as matting 1) can be carried out before subsequent handling.Cleaning Process 1 is the process cleaned to the dye solvent being attached in dyeing process on the surface of polyvinyl alcohol resin film. By carrying out matting 1, dyestuff can be suppressed and be transferred in the liquid for being subsequently used for handling.In matting 1, generally make Use water.For cleaning method, be preferably impregnated in the solution, can also by by the solution coating in polyethenol series tree Cleaned on adipose membrane.The time of cleaning is not particularly limited, preferably 1 second~300 seconds, more preferably 1 second~60 seconds.Clearly The temperature for the solvent washed in process 1 needs the temperature that will not be dissolved for hydrophilic macromolecule.Generally in 5 DEG C~40 DEG C progress Cleaning treatment.
After dyeing process or matting 1, it can enter to exercise polyvinyl alcohol resin film and contain crosslinking agent and/or water-fast The process of agent.As crosslinking agent, the boron compound such as boric acid, borax or ammonium borate can be used；Glyoxal or glutaraldehyde Deng polyaldehyde；The multicomponent isocyanate based compound of biuret form, isocyanurate type or end-sealed type etc.；The titanium such as titanyl sulfate system Compound；Etc., in addition, glycol glycidyl ethers, polyamideepichlorohydrin etc. can also be used.It is used as resistance to aquation Agent, can enumerate succinic acid peroxide, ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidylether, glycerine Diglycidyl ether, ammonium chloride or magnesium chloride etc., preferably use boric acid.Use at least one crosslinking agent above illustrated above And/or resistance to hydrated agent carries out making the process that polyvinyl alcohol resin film contains crosslinking agent and/or resistance to hydrated agent.It is molten as now Agent, preferably water, but it is not limited to this.In the process for making polyvinyl alcohol resin film contain crosslinking agent and/or resistance to hydrated agent In, for the crosslinking agent in solvent and/or resistance to hydrated agent contain concentration for, if using boric acid as example, relative to solvent Concentration is preferably the weight % of the weight % of 0.1 weight %~6.0, more preferably 1.0 weight %~4.0.Solvent temperature in the process Degree is preferably 5 DEG C~70 DEG C, more preferably 5 DEG C~50 DEG C.For making polyvinyl alcohol resin film contain crosslinking agent and/or water-fast The method of agent, is preferably impregnated in the solution, by the solution coating or can also smear (Tu works) in polyvinyl alcohol resin On film.Processing time in the process is preferably 30 seconds~6 minutes, more preferably 1 minute~5 minutes.But, make polyvinyl alcohol Resin film contains crosslinking agent and/or resistance to hydrated agent is not essential, and in the case of the desired shortening time, need not carry out In the case of crosslinking Treatment or resistance to hydration process, it is convenient to omit the treatment process.
Carrying out dyeing process, matting 1 or polyvinyl alcohol resin film is contained crosslinking agent and/or resistance to hydrated agent After process, stretching process is carried out.Stretching process is the process that polyvinyl alcohol mesentery is carried out to uniaxial tension.Drawing process can be with For any of wet tensile method or dry stretch process.
In the case of dry stretch process, in the case that stretching heating dielectric is air dielectric, preferably in air dielectric Temperature be normal temperature~180 DEG C under the conditions of stretched.Additionally, it is preferred that in humidity is 20%RH~95%RH atmosphere at progress Reason.As heating means, for example, region pulling method, roller heating pulling method, pressurization pulling method, infrared heating between roller Pulling method etc., but its drawing process is not limited to this.Stretching process can be 1 section of stretching, can also be by more than 2 sections it is many Duan Lashen is carried out.
In the case of wet tensile method, stretched in water, water-miscible organic solvent or its mixed solution.It is preferred that will Polyvinyl alcohol mesentery is immersed in the solution containing crosslinking agent and/or resistance to hydrated agent while carrying out stretch processing.As crosslinking agent, The boron compound such as boric acid, borax or ammonium borate can be used；The polyaldehyde such as glyoxal or glutaraldehyde；Biuret form, isocyanide The multicomponent isocyanate based compound of urea acid esters type or end-sealed type etc.；Titanium sub-group compounds such as titanyl sulfate etc., in addition, may be used also So that spent glycol glycidol ether, polyamideepichlorohydrin etc..As resistance to hydrated agent, can enumerate succinic acid peroxide, Ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether, ammonium chloride or chlorination Magnesium etc..Containing it is illustrated above it is at least one more than crosslinking agent and/or resistance to hydrated agent solution in stretched.Crosslinking agent Preferably boric acid.For the concentration of the crosslinking agent in stretching process and/or resistance to hydrated agent, such as preferably 0.5 weight %~15 Weight %, more preferably the weight % of 2.0 weight %~8.0.Stretching ratio is preferably 2 times~8 times, more preferably 5 times~7 times.It is right In draft temperature, preferably handled at 40 DEG C~60 DEG C, be more preferably 45 DEG C~58 DEG C.Stretching time is usually 30 seconds~20 Minute, more preferably 2 minutes~5 minutes.Wet tensile process can carry out 1 section of stretching, can also be by more than 2 sections multistages Stretch to carry out.
After having carried out stretching process because occasionally there are on film surface crosslinking agent and/or resistance to hydrated agent precipitation or The attachment of foreign matter, therefore the matting (hereinafter referred to as matting 2) cleaned to film surface can be carried out.Scavenging period Preferably 1 second~5 minutes.Cleaning method is preferably to be impregnated in cleaning solution, can also be by by solution coating or being applied to Cleaned on polyvinyl alcohol resin film.Both 1 section of cleaning treatment can be carried out, at the multistage that more than 2 sections can also be carried out Reason.The solution temperature of matting is not particularly limited, usually 5 DEG C~50 DEG C, preferably 10 DEG C~40 DEG C.
As the solvent used in treatment process so far, for example, water, dimethyl sulfoxide (DMSO), N- methyl Pyrrolidones；Methanol, ethanol, propyl alcohol, isopropanol, glycerine, ethylene glycol, propane diols, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol or three hydroxyls The alcohols such as methylpropane；The amine equal solvent such as ethylenediamine or diethylentriamine, but it is not limited to these.Furthermore it is also possible to use 1 Plant the mixture of the above solvent.Most preferred solvent is water.
After stretching process or matting 2, the drying process of film is carried out.Drying process can by spontaneously dry come Carry out, table can be carried out by the compression based on roller or using air knife or suction roll etc. to further improve drying efficiency The moisture in face removes, and/or can carried out air-supply drying.As drying process temperature, preferably it is dried at 20 DEG C~100 DEG C Handle, processing more preferably is dried at 60 DEG C~100 DEG C.The drying process time can be applicable 30 seconds~20 minutes, be preferably 5 Minute~10 minutes.
Further, polarization element of the invention preferably in 500nm≤λ≤560nm wavelength region transmitance be 2% with Under.Transmitance is less than 1% more preferably in 540nm≤λ≤550nm wavelength region.Maximum is luminous be output as 440nm~ 470nm blue led or blue-fluorescence pipe lights near 550nm with faint sometimes.In this case, in shading Have a light bias generation, thus preferred pair this luminous be controlled；For the display of the display, in above-mentioned wavelength region In the case of transmitance more than 2%, it is intended to can not obtain sufficient contrast, thus preferably transmitance be less than 2%, it is more excellent It is less than 1% to be selected in transmitance in 540nm≤λ≤550nm wavelength region.
In addition, can have polarized light property in above-mentioned wavelength region.In this case, preferably 500nm≤λ≤ Tc≤2% in 560nm wavelength region；Tc≤1% more preferably in 540nm≤λ≤550nm wavelength region.
Their manufacture method is not particularly limited, and can enumerate：Using in 500nm≤λ≤560nm wavelength region The polyvinyl alcohol mesentery of dichroic dye with polarized light property carries out the film of orientation, dichroic dye is coated on into friction The film or element that are orientated after on base material film after processing, make dichroic dye mix and be coated on liquid-crystalline resin to rub The film that is orientated or element after on base material film after erasure reason, dichroic dye is set to mix and be coated on liquid-crystalline resin The film or element that are orientated after on base material film by shared, dichroic dye is set at least to be stretched in single shaft direction The film of dyeing orientation has been carried out on film after orientation, has made the mixed with resin such as dichroic dye and plastics and at least enters in single shaft direction The film that stretching of having gone is orientated, in addition, can also enumerate following methods：By in 500nm≤λ≤560nm wavelength region Fitted in film of performance that transmitance is less than 2% etc. and do not have polarisation in 500nm≤λ≤560nm wavelength region On the polarizer of characteristic.The polyvinyl alcohol mesentery for being adsorbed with dichroic dye is preferably set to carry out the film of orientation, it is not There is the Tp in the wavelength region to 420nm≤λ≤490nm to cause damage.
Using dichroic dye as in the case of the dichroism pigment for above-mentioned polarization element, its dichroic dye does not have Be particularly limited to, for example, C.I. directly red 79, C.I. directly red 81, C.I. directly purple 9, C.I. directly purple 35, C.I. directly purple 57, C.I. directly indigo plant 67 etc..These can be shared with dichroic dye (A) group and/or dichroic dye (B), It is not limited to share one kind, two or more can also be shared.
The combined amount of these dichroic dyes is not particularly limited, and is commonly angled relative to dichroic dye (A) group and/or two colors The parts by weight of total amount 100 of property dyestuff (B), are the parts by weight of 25 parts by weight~300.
In addition, in the range of polarized light property is not hindered, dichroic dye of the invention can also use other dichroism Dyestuff.Be not particularly limited as such dichroic dye, for example, C.I. directly Huang 12, C.I. directly Huang 28, C.I. Direct Yellow 44 etc..In addition to dichroic dye illustrated above, other organic dyestuff can be shared as needed.It is mixed Composition and division in a proportion example is not particularly limited.
The so obtained polarization element for having used dichroic dye is suitable as the display polarization element.
During using iodo-complexes as the dichroism pigment of the polarization element for the present invention, preferably Tc (λ 460)≤Tc (λ 600), more preferably Tc (λ 460) ＜ Tc (λ 600).For the polarizer using known iodo-complexes, usual Tc (λ 460) >Tc (λ 600), in below wavelength 500nm scope it can not obtain high contrast values.In addition, can be obtained by improving concentration High contrast values, but Tp ＜ 30% can be caused, it is impossible to obtain sufficient brightness.Based on these reasons, the inclined of iodo-complexes is used The piece that shakes is not suitable as the polarizer for the display.Therefore, in the case of using iodo-complexes, preferably Tc (λ 460)≤Tc (λ600)。
Do not limited for the manufacture method using iodo-complexes and Tc (λ 460)≤Tc (λ 600) polarization element, example The film for making the polyvinyl alcohol mesentery for being adsorbed with iodo-complexes carry out orientation can such as be enumerated.
For the manufacture method and the film-forming method of polyvinyl alcohol resin of the polyvinyl alcohol resin of composition polarization element For, it is identical with the method described in using during dichroic dye.In addition, the degree of polymerization of polyvinyl alcohol resin is preferably generally 1, 000~10,000,1,500~5,000 are more preferably.
For above-mentioned polyvinyl alcohol resin film, implement to be swelled process first.When being swelled process with using dichroic dye Described method is identical.
It is swelled after process and implements dyeing process.Dyeing process is to polyvinyl alcohol using the solution containing iodine and iodide Resin film is handled.It is not particularly limited as the solvent of solution, preferably water.As iodide, for example, The alkali metal iodides compound such as KI；Ammonium iodide, cobaltous iodide or zinc iodide etc., but this is not limited to, preferably use iodate alkali Metallic compound, more preferably use KI.Iodine concentration is preferably the weight % of 0.0001 weight %~0.5, more preferably 0.001 The weight % of weight %~0.4.The concentration of iodide is preferably the weight % of 0.001 weight %~8.Solution temperature in the process is excellent Elect 5 DEG C~50 DEG C, more preferably 10 DEG C~40 DEG C, particularly preferably 20 DEG C~30 DEG C as.Being impregnated in time in solution can be with Appropriate regulation, was preferably adjusted according to 30 seconds~6 minutes, is more preferably 1 minute~5 minutes.For colouring method, preferably soak Stain, can also be by the way that the solution coating or be applied on polyvinyl alcohol resin film be carried out in the solution.
When carrying out iodine and iodide processing, crosslinking agent and/or resistance to hydrated agent can be added in the solution.Usually using crosslinking Agent.It is not particularly limited as crosslinking agent, it is often preferred that boric acid.For example, addition boric acid concentration be preferably 0.1 weight %~ 5.0 weight %, more preferably the weight % of 2.0 weight %~4.0.In addition, containing iodine, iodide, crosslinking agent and/or resistance to aquation In the case of the polyvinyl alcohol resin film of agent, it is not necessarily required to iodine, iodide, crosslinking agent and/or resistance to hydrated agent and directly contains In polyvinyl alcohol resin film, also including containing the situation in film in the form of reaction.
In addition, crosslinking agent treatment process can also be carried out while dyeing process is carried out as described above, but more preferably exist Crosslinking agent treatment process is carried out after dyeing process.Processing method now can be by using the solution containing crosslinking agent to dye The film obtained in color process is handled to carry out.Being preferably generally using this containing the method that cross-linking agent solution is handled to contaminate Method in the solution of film immersion after color or the method that the solution is coated with or smeared on film.The dipping also may be used To be carried out before stretching process, alternatively, it is also possible to be carried out together with stretching process.When pulling method is dry stretch process, preferably exist Crosslinking agent processing is carried out before stretching；When pulling method is wet tensile method, carried out preferably together with stretch processing.As crosslinking agent, It is identical with the crosslinking agent described in the crosslinking agent treatment process in dichroic dye.In addition, can be with this contains cross-linking agent solution Resistance to hydrated agent has coexisted.As resistance to hydrated agent, the resistance to hydrated agent phase described in the resistance to hydrated agent treatment process with dichroic dye Together.Contain concentration for the crosslinking agent in solvent, if being represented by taking boric acid as an example, the concentration relative to solvent is preferably 0.1 The weight % of the weight % of weight %~6.0, more preferably 1.0 weight %~4.0.In the process, in stretching process advance market condition Under solvent temperature be preferably 5 DEG C~60 DEG C, carry out before the stretching in the case of more preferably 5 DEG C~40 DEG C；Together with stretching Solvent temperature is more preferably 45 DEG C~58 DEG C during progress.Processing time in the process is preferably 30 seconds~6 minutes, is more preferably 1 minute~5 minutes.
Stretching process has dry stretch process and wet tensile method, as the example of its method, respectively with dichroic dye Method described in stretching process is identical.
After stretch processing, implement the processing carried out using the solution containing halide.The processing be with adjust tone and Improve the process for the purpose of polarized light property.Processing method is preferably the method by the film immersion after dyeing in the solution, also may be used To be the method for being coated with or smearing the solution on film.As halide, the iodate alkali gold preferably such as KI and sodium iodide Belong to compound；The iodide such as ammonium iodide, cobaltous iodide or zinc iodide；The alkali metal chloride compound such as potassium chloride and sodium chloride；Or chlorine Change the chlorides such as zinc, be preferably water solubility.More preferably iodide, more preferably alkali metal iodides compound, especially excellent Elect KI as.The concentration of halide is to make Tc (λ 460)≤Tc (λ 600) key factor, and its concentration is because of the difference of species It is different, it is generally the case that to be preferably the weight % of the weight %, more preferably 7.0 weight % of 6.0 weight %~15.0~12.0, enter One step is preferably the weight % of 8.0 weight %~10.0.Treatment temperature also because halide concentration it is different and different, for example preferably For 5 DEG C~55 DEG C, more preferably 20 DEG C~40 DEG C.Processing time also because halide concentration it is different and different, for example preferably For 1 second~5 minutes；If the stabilization of the face internal characteristic in view of light polarizing film, preferably 5 seconds~30 seconds.In addition, being drawn by wet type In the case of stretching method progress stretching process, halide processing can also be carried out together with stretching process, if but after stretch processing Carry out halide processing, then stay in grade, therefore preferably.
Be not particularly limited as the solvent of the processing solution in treatment process so far, for example, water, Alcohol series solvent or two alcohol series solvents etc..Furthermore it is also possible to use the solution, dimethyl sulfoxide (DMSO) and water for being mixed with water and alcohols The mixed solvent of water and water-soluble solvent as mixed solvent etc..Most preferably water.
The drying process of film is carried out after halide processing.The drying method institute of drying method and dichroic dye The method stated is identical.
The so obtained polarization element for having used iodo-complexes is suitable as the display polarization element.
For resulting polarization element, in its one side or two-sided setting protective clear layer as supporter, so that shape Into polarizer.For protective clear layer used in the polarization element for the film being orientated for carrying out polyvinyl alcohol mesentery, It can be set in the way of the coating layer based on polymer or in the way of the laminated layer of film.In addition, for for application type The protective clear layer of polarization element, the base material for coated substrates can be provided directly as protective clear layer or can will partially Optical element is transferred in film base material etc. and above sets protective layer.
It is used as protective clear layer, preferably high mechanical strength, the transparent polymer or film of good thermal stability.As saturating The material of bright protective layer, for example, acetyl cellulose resins as triacetyl cellulose (TAC), diacetyl cellulose Or its film；Acrylic resin or its film；Corvic or its film；Polyester resin or its film；Polyarylate resin or its film； Using cyclic olefin as ENB as the cyclic polyolefin resin of monomer or its film；Polyethylene, polypropylene, ring system have The polyolefin of ENB skeleton or its copolymer；Main chain or side chain be acid imide and/or the resin or polymer of acid amides or its Film；Etc..In addition, as protective clear layer, can also set with the resin of liquid crystal liquid crystal property or its film.The thickness of diaphragm is for example For 0.5 μm~200 μm or so.Pass through the same species in above-mentioned in more than 1 layer of one side or two-sided setting or variety classes tree Fat or film make polarizer.
As the material as protective clear layer, more preferably at least PET film is used in one side.In conventional LCD display In, from the aspect of LCD characteristic and polarizer itself display image, protective clear layer mainly uses high transparency and birefringence Few TAC film.In addition, also directly being used as phase retardation film of visual angle compensation film etc. in the one side of protective clear layer sometimes. On the other hand, using in the fluorescence excitation color crossover display terminal of the polarizer of the present invention, polarizer act as photoswitch work( Can, it is not necessary to which the polarizer of the present invention is used as picture display face.Thus, it is not necessary to use TAC film or the conduct of low-birefringence The expensive films such as phase retardation film of visual angle compensation film, more preferably using low cost, mechanical property be excellent and processability is good PET film.The birefringence of PET film is larger, when accordingly acting as double side support body, and transmitance is tended to decline, therefore is preferably used in list The one side of face supporter or double side support body.In display device, for the PET film as polarizer supporter configuration and Speech, preferably above and below polarizer the opposite side of liquid crystal layer is configured at respect to polarization element.In addition, to improve transmitance and raising For the purpose of cementability, the more preferably PET film with adhesive layer.Easily bonding PET film is not particularly limited, and can use commercially available Product, are more preferably provided with adhesive layer two-sided.
In addition, can set at least 1 layer on protective clear layer as needed has the refraction lower than protective clear layer The layer of the material of rate is used as antireflective protective clear layer.By forming antireflective protective layer, so that the transmission efficiency of light is improved, Higher contrast value and Tp values can be obtained.Do not limited especially for the material with the refractive index lower than protective clear layer Fixed, for example, organic based material such as acrylic resin, fluorine-type resin；The inorganic based material such as colloidal silica；Deng Deng these materials can also be shared.In addition, both can be reaction system or non-reaction system.For their processing Method is not particularly limited, and can enumerate vapour deposition method, sputtering method, various rubbing methods etc..In addition, as needed can also be transparent Laminated multi-layer hard conating, high refractive index layer etc. on protective layer.
In above-mentioned, in order that protective clear layer is fitted with polarization element and needs cement.It is not special as cement Limit, preferably polyethenol series cement.As polyethenol series cement, for example, Gohsenol NH-26 (days This synthesis society manufactures), Exceval RS-2117 (manufacture of KURARAY societies) etc., but be not limited to this.It can be added in cement Crosslinking agent and/or resistance to hydrated agent.Maleic anhydride-isobutylene copolymers can be used in polyethenol series cement, as needed The cement for being mixed with crosslinking agent can be used.As maleic anhydride-isobutylene copolymers, for example, Isobam#18 (manufacture of KURARAY societies), Isobam#04 (manufacture of KURARAY societies), ammonia are modified Isobam#104 (manufacture of KURARAY societies), ammonia and changed Property Isobam#110 (manufacture of KURARAY societies), imidizate Isobam#304 (manufacture of KURARAY societies), imidizate Isobam# 310 (manufactures of KURARAY societies) etc..Water-soluble polynary epoxide can be used in crosslinking agent now.Water-soluble many yuan of rings For example, Denacol EX-521 (manufacture of Nagase ChemteX societies), Tetrad-C (three well gas for oxygen compound Learn society's manufacture) etc..In addition, as the cement beyond polyvinyl alcohol resin, can also use polyurethane series, acrylic acid series, The so known cement of epoxy.In addition, for the purpose of improving the bonding force of cement or improve water resistance, can also be with The weight % of 0.1 weight %~10 or so concentration is simultaneously containing additives such as zinc compound, chloride, iodide.For addition Thing is not limited.After cement laminating protective clear layer, it is dried or is heat-treated at a proper temperature, so that Obtain polarizer.
In addition, adhesive can be used for the laminating of protective clear layer and polarization element.It is not special as adhesive Limit, as preferred example, acrylic adhesive can be enumerated.From the characteristics such as bonding strength, transmitance and integral thickness In terms of set out, its thickness can be selected arbitrarily, usually 5 μm~50 μm of scope, be preferably 10 μm~30 μm of scope.
The polarizer of the present invention can be the polarizer with supporter.In order to attach polarizer, supporter preferably has Planar portions, in addition to for optical applications, supporter is preferably glass products formed.As the material of glass, example can be enumerated Such as soda-lime glass (ソ ー ダ ガ ラ ス), pyrex, the inorganic basal disc being made up of crystal, the inorganic substrate being made up of sapphire Etc. the glass of inorganic system；Plastic plate of the organic systems such as acrylic compounds, makrolon etc., the glass of preferably inorganic system.Glass plate Thickness and size can be desired size.In addition, for the polarizer with glass, in order to further improve list Plate light transmittance, can be provided with antireflection layer on its glass surface.
In addition, in order to which the laminating of above-mentioned supporter and polarization element or polarizer can be used into cement, adhesive etc., It is not particularly limited, acrylic adhesive can be enumerated as preferred example.From characteristics such as bonding strength, transmitances and Set out in terms of integral thickness, its thickness can be selected arbitrarily, usually 5 μm~50 μm of scope, be preferably 10 μm~30 μm Scope.
So obtained polarization element of the invention and polarizer in 440nm≤λ≤470nm wavelength region Tp >= 30% and the wavelength region between any continuous 20nm in CR >=8,000, CR >=5,000 in remaining wavelength region, it is fitted Cooperate to turn using the fluorescence excitation color of the maximum luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm as light source Polarization element and polarizer used in switching display.
Embodiment
The present invention is described in more detail by the following examples, but the present invention is not limited to these embodiments.Need explanation , method is carried out as described below for the evaluation of the transmitance shown in embodiment.
Determined using spectrophotometer (Japan Spectroscopy Corporation manufactures " V-7100 ") during transmitance, in the outgoing of light Side, the illuminant-C light for enabling the transmitance 100% after visibility correction based on JIS-Z8701 (2 ° of visuals field of illuminant-C) incides survey Determine sample.
To the incident illuminant-C light of 2 polarizers of the invention, by according to the parallel mode of the absorption direction of principal axis of 2 polarizers Determine obtained parallel (parallel Nicolle) spectrophotometric transmittance and be set to Tp；Will be orthogonal according to the absorption direction of principal axis of 2 polarizers Mode determines obtained orthogonal (cross Nicols) spectrophotometric transmittance and is set to Tc.In addition, contrast is based on spectrophotometric transmittance Contrast, is expressed as the value being made up of CR=Tp/Tc.
Respective transmitance is determined by using spectrophotometer (Japan Spectroscopy Corporation manufactures " V-7100 ").
Embodiment 1
Saponification degree is existed for the polyvinyl alcohol resin film (KURARAY societies manufacture VF series) of more than 99% 75 μm of thickness Impregnated in 40 DEG C of warm water 3 minutes and carry out swelling treatment.The film immersion for carrying out swelling treatment is made in containing 0.04 weight % For 45 DEG C of the C.I. direct oranges 39,0.1 weight % sodium tripolyphosphates, 0.1 weight % saltcake of the pigment of dichroic dye (A) group The aqueous solution in, carry out pigment dyeing processing, make pigment absorption on polyvinyl alcohol mesentery.With water to being adsorbed with the film of pigment Cleaned, after cleaning, carry out 1 minute boric acid using 40 DEG C of the aqueous solution of the boric acid containing 2 weight % and handle.While will The film stretching obtained after boric acid processing is to 5.0 times, while being carried out 5 minutes in 55 DEG C of the aqueous solution containing the weight % of boric acid 3 Processing.The film for making the boric acid be obtained after handling keeps tense situation, while using the water of normal temperature handle within 15 seconds.After handling Obtained film carries out drying process in 9 minutes at 70 DEG C at once, so as to obtain the polarization element of 25 μm of thickness.For resulting inclined Optical element, uses PET film (the Toyo Boseki K.K's manufacture for 100 μm of thickness for being provided with two-sided adhesive layer Cosmoshine A4300), the acrylic adhesive of 20 μm of polyethenol series cement and thickness, according to PET/ adhesive linkages/ It is formed in as polarization element/adhesive layer/glass on thickness 1mm glass substrate and carries out lamination, progress is laminated to obtain Polarizer, is used as measure sample.
Embodiment 2
The use of 0.02 weight % dichroic dye (B) is the pigment shown in formula (1), formula (1) as adsorbed pigment In, R1、R2For hydrogen atom, the ratio by the HPLC n determined is：N=1 is that 33%, n=2 is that 65%, n=3 is 2%, except this with Outside, polarizer is made similarly to Example 1, is used as measure sample.
Embodiment 3
As adsorbed pigment, the C.I. using the 0.018 weight % pigment organized as dichroic dye (A) is direct In pigment shown in 39 and 0.015 weight % of the orange formula (1) as dichroic dye (B), formula (1), R1、R2For hydrogen atom, Ratio by the HPLC n determined is：N=1 is that 33%, n=2 is that 65%, n=3 is 2%, in addition, similarly to Example 1 Ground makes polarizer, is used as measure sample.
Embodiment 4
As adsorbed pigment, the C.I. using the 0.01 weight % pigment organized as dichroic dye (A) is direct The C.I. of pigment and 0.02 weight % shown in 39,0.01 weight % of the orange formula (1) as dichroic dye (B) is directly red 81, in formula (1), R1、R2For hydrogen atom, the ratio by the HPLC n determined is：N=1 is that 33%, n=2 is that 65%, n=3 is 2%, in addition, polarizer is made similarly to Example 1, be used as measure sample.
Embodiment 5
Saponification degree is existed for the polyvinyl alcohol resin film (KURARAY societies manufacture VF series) of more than 99% 75 μm of thickness Impregnated in 40 DEG C of warm water 3 minutes and carry out swelling treatment.By the film immersion for carrying out swelling treatment in containing the weight of boric acid 2.8 Measure and dyeing processing is carried out in %, the weight % of iodine 0.044, the weight % of KI 3.13 30 DEG C of the aqueous solution, pigment absorption is existed On polyvinyl alcohol mesentery.While by the film stretching for carrying out pigment dyeing to 5.0 times, while containing the weight %'s of boric acid 3.0 Carry out handling for 5 minutes in 50 DEG C of the aqueous solution.The film for making the boric acid be obtained after handling keeps tense situation, while containing iodate Complementary color processing in 20 seconds is carried out in the weight % of potassium 8.0 30 DEG C of the aqueous solution.The film obtained after processing is carried out 9 points at 70 DEG C at once Clock drying process, so as to obtain the polarization element of 25 μm of thickness.Use the PET for 100 μm of thickness for being provided with two-sided adhesive layer The acrylic acid of 20 μm of film (Toyo Boseki K.K manufacture Cosmoshine A4300), polyethenol series cement and thickness It is that adhesive exists resulting polarization element according to composition lamination as PET/ adhesive linkages/polarization element/adhesive layer/glass On thickness 1mm glass substrate, carry out lamination to obtain polarizer, be used as measure sample.
Comparative example 1
Using the acrylic adhesive of 20 μm of thickness by from commercially available liquid crystal TV set, (Sharp Corporation manufactures AQUOS/32 inches) take out, protective clear layer fit in thickness 1mm glass substrate for the iodine system polarizer of two-sided TAC film On, it is used as measure sample.
Comparative example 2
Complementary color processing in 20 seconds is carried out using 30 DEG C of the aqueous solution containing the weight % of KI 5.0, in addition, with implementation Example 4 similarly makes polarizer, is used as measure sample.
The each of obtained unit distance 5nm is measured to the measure sample obtained by embodiment 1~5 and comparative example 1~2 The Tp of the spectral photometry value of wavelength is shown in Figure 1, and its Tc is shown in Figure 2.The Tp of each wavelength is shown in table 4 in 420nm~490nm In, its contrast value is shown in Table 5, the Tc of each wavelength is shown in Table 6 in 500nm~560nm.In addition, showing conduct in table 7 The value of the embodiment 5 of iodine system polarizer and the Tc (460) of comparative example 1~2 and Tc (600).
[table 4]
[table 5]
[table 6]
[table 7]
Tc (460) [%] Tc (600) [%]
Embodiment 5 0.0018 0.0080
Comparative example 1 0.0062 0.0018
Comparative example 2 0.0046 0.0015
It can be seen from the result of Fig. 1~2 and table 4~5：For the polarization for having used dichroic dye of embodiment 1~4 Piece, in 420nm~490nm wavelength region, Tp is higher, contrast is higher, particularly in 440nm~470nm wavelength zone It is excellent in domain.Further, it can be seen from table 6：Embodiment 4 is in 500nm~560nm wavelength region, and Tc is relatively low.Understand：Its The band domain of the high-contrast of the polarizer for sharing dichroic dye (A) and dichroic dye (B) of middle embodiment 3 and 4 is wider, It is very excellent in 440nm~470nm wavelength region.In addition, for the iodine system polarizer of embodiment 5, Tc is understood according to table 7 (460)≤Tc (600), although the polarizer for having used dichroic dye of embodiment 1~3 is poor, but in 440nm~470nm Wavelength region in, obtained the result that Tp is higher, contrast is higher.
On the other hand, for common iodine system polarizer known to comparative example 1~2, Tc is understood according to table 7 (460)>Tc (600), it can be seen from the result of Fig. 1~2 and table 4~5：Its result be 420nm~490nm wavelength region, Particularly in below 460nm wavelength region, Tp is relatively low, contrast is also insufficient.
Industrial applicibility
The polarization element and polarizer of the present invention is excellent in the polarized light property of 440nm≤λ≤470nm wavelength region, its It may be used as being output as 440nm~470nm blue led or blue-fluorescence pipe as the fluorescence excitation color of light source so that maximum is luminous The polarization element and polarizer of crossover display terminal.

Claims (11)

1. a kind of polarization element, its be used for using the maximum luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm as The fluorescence excitation color crossover display terminal of light source, the polarization element is characterised by,
Tp >=30% in 440nm≤λ≤470nm wavelength region, and at least one arbitrary continuation in the wavelength region 20nm between wavelength region in CR >=8,000, CR >=5,000 in remaining wavelength region, and at least contain dichroism Pigment；Wherein, λ represents wavelength；Tp refers to point according to the parallel mode of its respective absorption axis when overlapping by 2 polarization elements Light transmission rate (transmitance during parallel Nicolle)；Tc refers to 2 polarization elements according to the orthogonal side of its respective absorption axis Spectrophotometric transmittance (transmitance during cross Nicols) when formula is overlapping；CR is the abbreviation of contrast, and its expression is made up of Tp/Tc Value；
Dichroism pigment at least contains the dichroic dye (B) represented by one kind and formula (1) in dichroic dye (A) group,
Dichroic dye (A) group：
C.I. direct orange 26
C.I. direct orange 39
C.I. direct orange 107
Dichroic dye (B)：
[changing 1]
In formula, R1、R2Hydrogen atom, low alkyl group, lower alkoxy are represented independently of one another；N represents n=1~3.
2. polarization element as claimed in claim 1, it is characterised in that in 420nm≤λ ＜ 440nm wavelength region, Tp >= 30% and CR >=1,500.
3. polarization element as claimed in claim 1 or 2, it is characterised in that in 470nm ＜ λ≤490nm wavelength region, Tp >=30% and CR >=1,000.
4. polarization element as claimed in claim 1 or 2, it is characterised in that in 500nm≤λ≤560nm wavelength region, Transmitance is less than 2%.
5. polarization element as claimed in claim 3, it is characterised in that in 500nm≤λ≤560nm wavelength region, is passed through Rate is less than 2%.
6. a kind of polarization element, its be used for using the maximum luminous blue led or blue-fluorescence pipe for being output as 440nm~470nm as The fluorescence excitation color crossover display terminal of light source, the polarization element is characterised by,
Tp >=30% in 440nm≤λ≤470nm wavelength region, and at least one arbitrary continuation in the wavelength region 20nm between wavelength region in CR >=8,000, CR >=5,000 in remaining wavelength region, and at least contain dichroism Pigment, dichroism pigment is iodo-complexes, and Tc (λ 460)≤Tc (λ 600),
Herein, λ represents wavelength；Tp refers to point according to the parallel mode of its respective absorption axis when overlapping by 2 polarization elements Light transmission rate (transmitance during parallel Nicolle)；Tc refers to 2 polarization elements according to the orthogonal side of its respective absorption axis Spectrophotometric transmittance (transmitance during cross Nicols) when formula is overlapping；CR is the abbreviation of contrast, and its expression is made up of Tp/Tc Value；Tc (λ 460) be by 2 polarization elements according to the orthogonal mode of its respective absorption axis it is overlapping when (during cross Nicols) The spectrophotometric transmittance at 460nm；Tc (λ 600) is according to the orthogonal mode weight of its respective absorption axis by 2 polarization elements The spectrophotometric transmittance at 600nm when folded (during cross Nicols).
7. polarization element as claimed in claim 6, it is characterised in that in 420nm≤λ ＜ 440nm wavelength region, Tp >= 30% and CR >=1,500.
8. polarization element as claimed in claims 6 or 7, it is characterised in that in 470nm ＜ λ≤490nm wavelength region, Tp >=30% and CR >=1,000.
9. a kind of polarizer, it is set at least one side by the polarization element described in any one in claim 1~8 Support film.
10. polarizer as claimed in claim 9, wherein, at least one side of support film is PET film.
11. a kind of polarizer with inorganic substrate, it is characterised in that lamination is had the right the appointing of requirement 1~8 on inorganic substrate The polarizer described in polarization element or claim 9 or 10 described in one.
CN201280035152.4A 2011-07-22 2012-07-13 Polarization element and polarizer Expired - Fee Related CN103649793B (en)

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Families Citing this family (12)

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KR102118004B1 (en) * 2013-06-03 2020-06-02 니폰 가야꾸 가부시끼가이샤 Polarizing element and polarizing plate for display device having blue light emitting element
JP6853010B2 (en) * 2015-11-06 2021-03-31 日本化薬株式会社 Achromatic polarizing element, and achromatic polarizing plate and liquid crystal display device using this
CN110366691B (en) 2017-03-03 2022-02-18 日本化药株式会社 Image display device
US10585306B2 (en) 2017-07-06 2020-03-10 Shenzhen China Star Optoelectronics Technology Co., Ltd Liquid crystal panel, liquid crystal display, and method for manufacturing a yellow-dye polarizer
CN107315276A (en) * 2017-07-06 2017-11-03 深圳市华星光电技术有限公司 The preparation method of liquid crystal panel, liquid crystal display and weld polaroid
WO2019022212A1 (en) * 2017-07-28 2019-01-31 日本化薬株式会社 Polarized-light-emitting element, polarized-light-emitting plate, display device, and method for manufacturing polarized-light-emitting element
JP7200108B2 (en) 2017-07-28 2023-01-06 日本化薬株式会社 Stilbene compound or salt thereof, polarizing film, polarizing plate and display device
JP2019056904A (en) * 2017-09-20 2019-04-11 日本化薬株式会社 Plane polarized light emitting element
JP2019086622A (en) * 2017-11-06 2019-06-06 株式会社ポラテクノ Polarizing member and head-up display device having the same
WO2019124161A1 (en) * 2017-12-22 2019-06-27 日本化薬株式会社 Azo compound or salt thereof, and polarizing element, polarizing plate, and display device comprising same
WO2021010100A1 (en) * 2019-07-16 2021-01-21 住友化学株式会社 Optical laminate
WO2024085142A1 (en) * 2022-10-18 2024-04-25 株式会社クラレ Polyvinyl alcohol film and stretched film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002174728A (en) * 2000-12-07 2002-06-21 Nitto Denko Corp Polarizing plate and liquid crystal display device using the same
CN101460571A (en) * 2006-06-01 2009-06-17 日本化药株式会社 Azo compound and salt thereof, and dye-containing polarizing film comprising the compound or salt
JP2011053234A (en) * 2008-01-11 2011-03-17 Nippon Kayaku Co Ltd Dye-based polarizer, polarizing plate, and method for producing them

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3306696A1 (en) 1983-02-25 1984-08-30 Bayer Ag, 5090 Leverkusen REACTIVE DYES
JP2002022950A (en) * 2000-07-10 2002-01-23 Nitto Denko Corp Polarizing film, polarizing plate and liquid crystal display device
JP2002258043A (en) * 2001-03-02 2002-09-11 Nitto Denko Corp Polarizing plate and liquid crystal display device using the same
JP2002258042A (en) * 2001-03-02 2002-09-11 Nitto Denko Corp Polarizing plate and liquid crystal display device using the same
CN100419029C (en) 2003-04-16 2008-09-17 日本化药株式会社 Azo compound and salt thereof
JP4499131B2 (en) * 2007-04-18 2010-07-07 株式会社クラレ Manufacturing method of polarizing film
JP5196651B2 (en) * 2008-11-27 2013-05-15 日東電工株式会社 Iodine polarizing film and method for producing the same
JP2011002775A (en) * 2009-06-22 2011-01-06 Hitachi Displays Ltd Liquid crystal display

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002174728A (en) * 2000-12-07 2002-06-21 Nitto Denko Corp Polarizing plate and liquid crystal display device using the same
CN101460571A (en) * 2006-06-01 2009-06-17 日本化药株式会社 Azo compound and salt thereof, and dye-containing polarizing film comprising the compound or salt
JP2011053234A (en) * 2008-01-11 2011-03-17 Nippon Kayaku Co Ltd Dye-based polarizer, polarizing plate, and method for producing them

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