CN103649793A - Polarization element and polarization plate - Google Patents
Polarization element and polarization plate Download PDFInfo
- Publication number
- CN103649793A CN103649793A CN201280035152.4A CN201280035152A CN103649793A CN 103649793 A CN103649793 A CN 103649793A CN 201280035152 A CN201280035152 A CN 201280035152A CN 103649793 A CN103649793 A CN 103649793A
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- CN
- China
- Prior art keywords
- polaroid
- wavelength region
- polarization element
- film
- dichroic dye
- Prior art date
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Images
Classifications
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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
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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
-
- 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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- Optics & Photonics (AREA)
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Abstract
The invenstion relates to a polarization plate. To provide the polarization plate that is suitable for use in a fluorescence excitation color conversion display that uses a blue LED or a blue fluorescent tube with a maximum luminescent output of 440nm-470nm as the light source, and that is characterized by having high contrast, low light leakage, and high transmittance when transmitting light. Provided are a polarization element and the polarization plate characterized by having the following: a TP of >=30% in the 440nm<=lambda<=470nm wavelength region, CR of >=8,000 in a random continuous 20nm range wavelength region and CR of >=5,000 in the remaining wavelength regions, and at least a dichromatic color element.
Description
Technical field
The present invention relates to polarization element and use its polaroid.
Background technology
Polarization element is normally manufactured by making to be adsorbed on polyvinyl alcohol resin film and to be orientated as the iodo-complexes of dichromatism pigment or dichroic dye.The diaphragm consisting of triacetyl cellulose etc. is fitted in across cement layer at least one side of this polarization element, thereby form polaroid.Therefore polaroid has light transmission/shielding function, becomes the basic comprising assembly of display device such as having the liquid crystal of light switch function and liquid crystal display (LCD).The suitable application area of LCD also extends to the broad range such as instrumentation machine of notebook computer, word processor, liquid crystal projection apparatus, liquid crystal TV set, vehicle mounted guidance, mobile phone and indoor and outdoor from small-sized machines such as the counter at initial stage and clock and watch, and can under the extensive condition of low temperature～high temperature, low humidity～high humility, low light quantity～high light quantity, use.Therefore, require the polaroid of the high and excellent in te pins of durability of polarizing properties.In addition, using iodo-complexes to be called as iodine as the polaroid of dichromatism pigment is polaroid; On the other hand, using dichroic dye to be called as dyestuff as the polaroid of dichromatism pigment is polaroid.Among them, from the aspect of optical characteristics excellence, often using iodine is polaroid.For dyestuff is polaroid, if compare thering is the polaroid of identical degree of polarization, dyestuff is that the transmitance of polaroid is polaroid lower than iodine, be that it has the problem that contrast is low, therefore but it has high-fire resistance, the such feature of high humidity heat durability, be used in color liquid crystal projector etc. (patent documentation 1).
Now, the light source in the LCD of take headed by liquid crystal TV set is the light source that uses CCFL or high-pressure sodium lamp, further, in recent years as the light emitting diode (LED) of patent documentation 2, patent documentation 3 popularize, White LED is widely used.For having used the polaroid of these light sources, used as known common neutral gray iodine polaroid.Iodine polaroid has the high feature of contrast in wider wavelength region may, for CCFL or high-pressure sodium lamp and White LED etc., is useful.
In addition, the effect of the liquid crystal panel consisting of polaroid and liquid crystal is not only through light and the such light switch function of shield light, in liquid crystal panel, also has both and has color filter, and performance shows the effect of image.As its research topic, have such problem as described below: due to the direction of orientation of liquid crystal, thereby can there is light leak according to the difference of watching the angle of image, make to be difficult to see image, be that angle of visibility is narrow.For the kind of liquid crystal, can take the various ways such as VA type (vertical orientating type), TN type (twisted nematic), IPS (plane inner switching type), no matter although the degree of its angle of visibility exists different, all there is the problem that angle of visibility is narrow in which kind of mode.In order to make up the narrow of this angle of visibility, the optical compensation films such as TAC (triacetyl cellulose) film have been widely used, wherein, these optical compensation films are by making PC (polycarbonate) film, COP (cycloolefin) film, discotic mesogenic be orientated and be coated with at specific direction and form.
As the display that has used liquid crystal technology, known in the past have a following display (hereinafter referred to as fluorescence excitation color conversion display), wherein, for example use blue LED as backlight, and possess and replace color filter because of the blue light fluorophor that sends shades of colour light that is excited.For example disclosed in patent documentation 4.The liquid crystal indicator of this phosphor excitation color conversion mode carries out wavelength conversion by fluorophor to the light being penetrated by backlight, carries out desired color show by resulting fluorescence.This liquid crystal indicator is different from the liquid crystal indicator of color filter mode, owing to not existing because of the optical absorption loss due to color filter, therefore has the high such feature of light utilization ratio.In addition, it is characterized in that, do not exist in LCD in the past as the narrow such problem of angle of visibility of problem, the image that can obtain high image quality shows.For such light source, in order to improve the luminescence efficiency of fluorophor, used the light source of blue region.The light source of blue region has been used blue led or the blue-fluorescence pipe of the maximum luminous 440nm of being output as～470nm.
Generally, for flat-panel monitor, in the picture of whole reflections within the scope of whole angle of visibilities, contrast need to be for more than 50.More preferably, in picture, contrast need to be for more than 100." picture in contrast " refers under the state that shows a reflection ratio of bright pixel and the brightness of dark pixel.It should be noted that the ratio of the brightness of brightness when common used " panel contrast " is complete white demonstration during with complete black demonstration.But, carry out the such reflection of complete white demonstration or complete black demonstration and exist hardly in reality.In addition, if the sense of fatigue of the too high eyes of contrast can strengthen.Therefore, as the specification that requires of the contrast based on ergonomics, recommend that " contrast in picture " is more than 50, more preferably more than 100 (non-patent literature 1).
In needed picture, contrast is according to watching that the difference of the periphery illumination of flat-panel monitor changes.That is, periphery illumination is brighter, and in needed picture, contrast is less; Periphery illumination is darker, and in needed picture, contrast is larger.When periphery illumination is changed within the scope of 0lux～500lux, in needed picture, the value of contrast is shown in table 1.
[table 1]
Feature as average signal level ASL (Average Signal Level) or the average brightness level ALL (Average Luminance Level) of common television broadcasting, reported average out to ASL40%, ALL20% left and right, scope is ASL20%～60% left and right, ALL5%～40% left and right.It is reported: while watching these reflections by being of a size of the televisor of 65 inches, at common living environment, be under illumination 180lux, while watching with viewing distance 3H (3 times of distances when the height of televisor is made as to H), as the most preferred high-high brightness of televisor, be 240cd/m
2(non-patent literature 2).Herein, when common parlor periphery illumination is 180lux, in parlor, in picture, contrast is more than 50, need to be for more than 200 according to contrast in the picture in the known darkroom of table 1.
The condition that in picture, contrast becomes minimum is when picture integral body shows darker reflection.While showing the darkest reflection, 5% left and right (non-patent literature 3) that the brightness that can say bright pixel in picture is high-high brightness.High-high brightness is 240cd/m
2the situation of display under, in picture, the brightness of bright pixel is 12cd/m
2left and right.Under such condition, in order to make contrast in picture, be more than 200, the brightness of the dark pixel in picture need to be suppressed to 0.06cd/m
2below left and right.That is in order to meet the brightness of the bright pixel in picture, be, 240cd/m
2, the dark pixel in picture brightness be 0.06cd/m
2above-mentioned condition like this, panel contrast need to be 4,000.It should be noted that the ratio of transmitance when transmitance during light transmission when panel contrast represents to utilize a pair of polaroid to clip liquid crystal panel (parallel Nicol) and light shield (cross Nicols).
In picture in fluorescence excitation color conversion display, the relation of contrast, panel contrast and polaroid contrast is shown in table 2.
[table 2]
| CR in picture | 50 | 100 | 200 | 250 | 300 | 350 |
| High-high brightness [cd/m 2] | 240 | 240 | 240 | 240 | 240 | 240 |
| The 5%[cd/m of full brightness 2] | 12 | 12 | 12 | 12 | 12 | 12 |
| Require black level [cd/m 2] | 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 |
| Polaroid CR | 2,000 | 4,000 | 6,000 | 8,000 | 10,000 | 15,000 |
Known according to table 2: in the situation that is 4,000 in panel contrast, polaroid contrast need to be 6,000.It should be noted that, the polaroid contrast in table 2 represents the ratio of the energy transmitance Ep of the light under light transmission state (during the parallel Nicol of open mode/polaroid) and the energy transmitance Ec of the light under light shield state (during closed condition/polaroid cross Nicols).The energy transmitance Ep of light represents to incide in the provision wavelengths scope under light transmission state the energy of the light quantity (blue light) of the light of luminescent coating unit area.The energy transmitance Ec of the light under masked state represents to incide in the provision wavelengths scope under light shield state the energy of the light quantity (blue light) of the light of luminescent coating unit area.
In the mode of fluorescence excitation color conversion display, by being incided, blue light on fluorophor, generates R, G, each coloured light of B, the value that the light splitting radiance of the light of the brightness of display device after by light-emitting phosphor is multiplied by visibility determines, but the projectile energy of the light splitting radiance of the light that autofluorescence body sends and the blue light of excited fluophor is proportional, and this is well-known.In addition, even can there is too to see through the impact of the depolarization that liquid crystal panel causes etc. in blue light.For the above reasons, the polaroid contrast (Ep/Ec) based on the needed energy transmitance of a pair of polaroid can think that with the polaroid contrast (Tp/Tc) based on spectrophotometric transmittance be of equal value.It should be noted that, Tp refers to the spectrophotometric transmittance (transmitance during parallel Nicol) when 2 polarization elements are overlapping according to the parallel mode of its absorption axes separately; Tc refers to the spectrophotometric transmittance (transmitance during cross Nicols) when 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately.But the emission wavelength of fluorophor depends on the shown band structure of fluorescent material, be not therefore the excitating light strength that is conceived to specific wavelength, and need to estimate the energy integral body of the light of excited fluophor.
According to foregoing, the polaroid contrast (Ep/Ec) of the energy transmitance based on light is 6,000 o'clock, particularly in the luminous output area of maximum of backlight arbitrarily between wavelength, polaroid contrast (Tp/Tc) based on spectrophotometric transmittance need to be for being greater than 6,000 numerical value, preferably contrast (Tp/Tc) is 8,000.In addition, in order to make the contrast (Ep/Ec) of the energy transmitance based on light, be higher numerical value, also needing to make the polaroid contrast (Tp/Tc) based on spectrophotometric transmittance is higher numerical value.
Can say more preferably under 300lux contrast >=100 in picture.In this case, according to table 1 and table 2, contrast >=350, polaroid contrast >=15 based on energy transmitance in picture in darkroom, 000, as the polaroid contrast based on spectrophotometric transmittance, particularly in the luminous output area of maximum of backlight arbitrarily between wavelength, it is more than 20,000 needing contrast.
In addition, the liquid crystal indicator of mode showed the Luminance Distribution of the directive property of general reflection backlight in the past, and the mode of fluorescence excitation color conversion display is characterised in that, utilize the luminous (of the isotropy Deng Fang development light based on fluorophor), angle of visibility is wider.On the other hand, the words that directive property is low surface brightness reduce.Can say that when being changed to full width at half maximum 45 and being spent by full width at half maximum 30 degree, front face brightness probably reduces half.
For the image signal of common televisor and video, in 0～255 gray scale that conventionally can show with 8bit, by 16～235 gray scales, show.But, can use 255 gray scales being called as under the brightness amplification mode of ultrawhite pattern.During complete white demonstration, in 235 gray scales, can obtain 400cd/m
2the situation of brightness under, the brightness while showing 255 gray scale under ultrawhite pattern can obtain the 487cd/m of approximately 1.2 times when being set as γ 2.2
2.The comparison of the maximum display brightness under full white luminance and ultrawhite pattern has been shown in table 3.In the mode of fluorescence excitation color conversion display, the value of the energy transmitance Ep of the light under the light transmission state of known polaroid (during parallel Nicol) is 30% when above, for most preferred brightness is 240cd/m
2.More than obtaining Ep30%, the transmitance Tp during in the parallel Nicol of spectrophotometric transmittance is necessary for more than 30%.
[table 3]
Known common neutral gray iodine polaroid contrast in wider wavelength region may is higher, but for the luminous blue-light source region that is output as 440nm～470nm fluorescence excitation color conversion display, maximum, light leak is more and cannot obtain sufficient contrast, and brightness is also not enough.When the polaroid as in fluorescence excitation color conversion display, in order to obtain high-high brightness 240cd/m
2and require Ep>=30% and in order to obtain 240cd/m
2high-high brightness and 200 more than darkroom in picture contrast and require polaroid contrast (Ep/Ec) 6,000, also there is no to reach so far the polaroid of above-mentioned requirements.
Prior art document
Patent documentation
Patent documentation 1: No. 2001-027708, TOHKEMY
Patent documentation 2: No. 3585097th, Jap.P.
Patent documentation 3: No. 4686644th, Jap.P.
Patent documentation 4: No. 2009-134275, TOHKEMY
Non-patent literature
Non-patent literature 1:SID ' 03Digest p.779
Non-patent literature 2: electronic information communication association paper will (the Electricity Ziqing Reported Theory of Communications Society literary composition Chi), J91-A (6), pp.630-638 (2008)
Non-patent literature 3:JJAP vol.46,3B, 2007, p.1358
Summary of the invention
Invent problem to be solved
As mentioned above, as for take the blue led of the luminous 440nm of the being output as～470nm of maximum or the polaroid of the fluorescence excitation color conversion display that blue-fluorescence pipe is light source, known iodine was that polaroid exists relatively low etc. and so on the problem of this wavelength region may transmitance lower, can there is light leak or light transmission time of contrast in the past, therefore cannot obtain showing fully image.Therefore, problem of the present invention is to provide a kind of polarization element and polaroid that is suitable for this display, it is characterized in that this polarization element and polaroid contrast is high and light leak is few, transmitance during light transmission is high.
Solve the means of problem
In order to solve above-mentioned problem, the inventor conducts in-depth research, found that at least contain dichromatism pigment, high polarization element and the polaroid of transmitance in the contrast of the wavelength region may of 440nm≤λ≤470nm during high and light transmission can solve above-mentioned problem, thereby complete the present invention.
That is, the present invention relates to:
(1) a kind of polarization element, it is for take the blue led of the luminous 440nm of the being output as～470nm of maximum or the fluorescence excitation color conversion display that blue-fluorescence pipe is light source, this polarization element is characterised in that, Tp >=30% in the wavelength region may of 440nm≤λ≤470nm, and CR >=8 in the wavelength region may between the 20nm of the arbitrary continuation in this wavelength region may, 000, CR >=5 in remaining wavelength region may, 000, and at least contain dichromatism pigment.
Herein, λ represents wavelength; Tp refers to the spectrophotometric transmittance (transmitance during parallel Nicol) when 2 polarization elements are overlapping according to the parallel mode of its absorption axes separately; Tc refers to the spectrophotometric transmittance (transmitance during cross Nicols) when 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately; CR is the abbreviation of contrast, and it represents the value consisting of Tp/Tc.
(2) polarization element as described in (1), is characterized in that, in the wavelength region may of 420nm≤λ < 440nm, and Tp >=30% and CR >=1,500.
(3) polarization element as described in (1) or (2), is characterized in that, in the wavelength region may of 470nm < λ≤490nm, and Tp >=30% and CR >=1,000.
(4) polarization element as described in any one of (1)～(3), wherein, dichromatism pigment at least contains a kind of in dichroic dye (A) group and/or dichroic dye (B) that formula (1) is represented.
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, R
1, R
2represent independently of one another hydrogen atom, low alkyl group, lower alkoxy; N represents n=1～3)
(5) polarization element as described in any one of (1)～(4), is characterized in that, in the wavelength region may of 500nm≤λ≤560nm, transmitance is below 2%.
(6) polarization element as described in any one of (1)～(3), is characterized in that, dichromatism pigment is iodo-complexes, and Tc (λ 460)≤Tc (λ 600).
The spectrophotometric transmittance at 460nm place of (during cross Nicols) when herein, Tc (λ 460) is that 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately; The spectrophotometric transmittance at 600nm place of (during cross Nicols) when Tc (λ 600) is that 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately.
(7) polaroid described in any one of (1)～(6), wherein, this polaroid is to form by support film being set at least one side of polarization element.
(8) polaroid as described in (7), wherein, at least one side of support film is PET (polyester) film.
(9) with a polaroid for inorganic substrate, it is characterized in that, on inorganic substrate, lamination has polarization element or (7) or (8) the described polaroid described in any one of (1)～(6).
Invention effect
Polarization element of the present invention and use its polaroid to have high polarity energy in the wavelength region may of 440nm≤λ≤470nm, can provide and be applicable to take the blue led of 440nm～470nm or the polaroid of the fluorescence excitation color conversion display that blue-fluorescence pipe is light source.
Accompanying drawing explanation
Fig. 1 is that unit distance is the Tp of spectral photometry value of each wavelength of 5nm
Fig. 2 is that unit distance is the Tc of spectral photometry value of each wavelength of 5nm
Embodiment
For polarization element of the present invention, Tp >=30% in the wavelength region may of 440nm≤λ≤470nm, and in this wavelength region may CR >=8 in the wavelength region may between the 20nm of arbitrary continuation, 000, CR >=5 in all the other wavelength region may, 000.By using such polarization element of the present invention, can make take the blue led of the luminous 440nm of the being output as～470nm of maximum or the fluorescence excitation color conversion display that blue-fluorescence pipe is light source to obtain sufficient brightness and contrast.Demonstration for this display, in the wavelength region may of 440nm≤λ≤470nm, CR < 8 in wavelength region may between the 20nm of arbitrary continuation, 000, CR < 5 in all the other wavelength region may, under 000 such condition, tend to obtain sufficient contrast, therefore in the wavelength region may between the 20nm of arbitrary continuation, need CR >=8,000, in all the other wavelength region may, need CR >=5,000.Preferably, CR >=10 in the wavelength region may in the wavelength region may of 440nm≤λ≤470nm between the 20nm of arbitrary continuation at least, 000, more preferably CR >=15,000.Further preferably, for the wavelength region may of 450nm≤λ≤460nm, CR >=20,000.About contrast value, by reducing the veneer transmitance of polarization element, can improve CR value, but in this case, Tp value also can reduce and cannot obtain sufficient brightness.Under the condition of Tp < 30%, tend to obtain sufficient brightness; Under Tp >=30% condition, light utilization ratio is excellent, can reduce power consumption.Preferably Tp >=31%, more preferably Tp >=32%.
Further, for polarization element of the present invention, preferably in the wavelength region may of 420nm≤λ < 440nm, Tp >=30% and CR >=1,500.The weak light preferably blue led of the luminous 440nm of the being output as～470nm of maximum or blue-fluorescence pipe further being had at short wavelength side is controlled, demonstration for this display, CR < 1 in above-mentioned wavelength region may, under 500 conditions, contrast is tended to reduce, preferred CR >=1,500, more preferably CR >=3,000, further preferred CR >=5,000.In addition, same with the wavelength region may of above-mentioned 440nm≤λ≤470nm, in the situation of Tp < 30%, tend to obtain sufficient brightness; In the situation of Tp >=30%, the utilization ratio of light is excellent, can reduce power consumption.Preferably Tp >=31%, more preferably Tp >=32%.
Further, for polarization element of the present invention, preferably in the wavelength region may of 470nm < λ≤490nm, Tp >=30% and CR >=1,000.The weak light preferably blue led of the luminous 440nm of the being output as～470nm of maximum or blue-fluorescence pipe further being had at long wavelength side is controlled, demonstration for this display, in above-mentioned wavelength region may, under CR < 1,000 condition, contrast is tended to reduce; Preferred CR >=1,000, more preferably CR >=2,500, further preferred CR >=4,000.In addition, same with the wavelength region may of above-mentioned 440nm≤λ≤470nm, in the situation of Tp < 30%, tend to obtain sufficient brightness; In the situation of Tp >=30%, the utilization ratio of light is excellent, can reduce power consumption.Preferably Tp >=31%, more preferably Tp >=32%.
Polarization element of the present invention at least contains dichromatism pigment.As dichromatism pigment, can enumerate such as iodo-complexes, dichroic dye etc.
While using dichroic dye as dichromatism pigment for polarization element of the present invention, preferably use at least one and/or the represented dichroic dye (B) of 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 2]
(in formula, R
1, R
2represent independently of one another hydrogen atom, low alkyl group, lower alkoxy; N represents 1～3)
Dichroic dye (A) group is all to show high dichromatic dyestuff, it is characterized in that, the wavelength (λ max) that shows maximum-contrast value is 420nm≤λ max≤460nm.Wherein, more preferably use C.I. direct orange 39.
Dichroic dye (B) shown in formula (1) is to show high dichromatic dyestuff, it is characterized in that, the wavelength (λ max) that shows maximum-contrast value is 450nm≤λ max≤470nm.
In formula (1), R
1, R
2be preferably hydrogen atom.In addition, be preferably the potpourri that the compound by n=1～3 forms, the weight of the compound of the preferred n=2 of its ratio with respect to the ratio of the total weight of the compound of n=1 and n=3 be more than 55%, more preferably more than 65%, more preferably more than 75%, most preferably be more than 85%.
In addition, the dichroic dye (B) shown in formula (1) can obtain by the method described in WO2007/138980 is synthetic.
More preferably share at least one and dichroic dye (B) in dichroic dye (A) group.Generally, the optical characteristics of the polarization element obtaining than using dichroic dye separately respectively, the optical characteristics of the polarization element that share different dichroic dyes and obtain is tended to decline, on the other hand, at least one and the dichroic dye (B) that in the present invention, share in dichroic dye (A) group can not hinder characteristic separately, result is that the characteristic of λ max is improved, and can in wide band, embody high characteristic.Resulting polarization element is characterised in that, its λ max is 440nm≤λ max≤470nm; The polarization element obtaining is compared with using respectively dichroic dye (A) group or dichroic dye (B), the polarization element that share different dichroic dyes and obtain can obtain more high contrast values in equal Tp situation, in the situation that equal contrast value can obtain higher Tp value.In addition, share different dichroic dyes and the polarization element that obtains can obtain high contrast values in wider wavelength region may.
While share at least one and the dichroic dye (B) in dichroic dye (A) group, for dichroic dye (A) group and the mixing ratio of dichroic dye (B), be not particularly limited, but with respect to dichroic dye (A) group 100 weight portions, dichroic dye (B) is 25 weight portion～400 weight portions conventionally; Preferably, with respect to dichroic dye (A) group 100 weight portions, dichroic dye (B) is 50 weight portion～200 weight portions.
Use the manufacture method of the polarization element of these dichroic dyes to be not particularly limited, for example can enumerate: make absorption have the polyvinyl alcohol mesentery of dichroic dye to be orientated the film forming, after being coated on the base material film after friction treatment, dichroic dye carried out film or the element of orientation, dichroic dye mixed with liquid-crystalline resin and coat on the base material film after friction treatment after carried out film or the element of orientation, dichroic dye is mixed with liquid-crystalline resin and coat rear film or the element that has carried out orientation by sharing (sharing) on base material film, make dichroic dye at least in single shaft direction, carry out having carried out on the film after stretch orientation the film of dyeing orientation, make the mixed with resin such as dichroic dye and plastics and at least in single shaft direction, carried out the film etc. of stretch orientation.Be preferably and make absorption have the polyvinyl alcohol mesentery of dichroic dye to be orientated the film forming, it can obtain high contrast values.
For the manufacture method that forms the polyvinyl alcohol resin of polarization element, be not particularly limited, can use known method manufacture.As the manufacture method of polyvinyl alcohol resin, for example can be by being that resin carries out saponification and obtains to polyvinyl acetate.As polyvinyl acetate, be resin, except the polyvinyl acetate of the homopolymer as vinyl acetate, can also enumerate vinyl acetate with can be with the multipolymer of other monomers of its copolymerization etc.As other monomers with vinyl acetate copolymerization, can enumerate such as unsaturated carboxylic acid class, olefines, vinyl ethers or unsaturated sulfonic acid class etc.The saponification degree of polyvinyl alcohol resin is preferably 85 % by mole～100 % by mole conventionally, more preferably more than 95 % by mole.This polyvinyl alcohol resin can further carry out modification, such as using by the polyvinyl formal after aldehydes modification or Pioloform, polyvinyl acetal etc.In addition, the degree of polymerization of polyvinyl alcohol resin is preferably 1,000～10,000, more preferably 1,500～7,000 conventionally.
Described polyvinyl alcohol resin is filmed to the film forming and is used as base film (former anti-Off ィ Le system).Film-forming method for polyvinyl alcohol resin is not particularly limited, and can use known method to be filmed.In this case, polyvinyl alcohol resin film can contain glycerine, ethylene glycol, propylene glycol or low molecular poly etc. as plastifier.Plasticising dosage is preferably 5 % by weight～20 % by weight, 8 % by weight～15 % by weight more preferably.Thickness for the base film consisting of polyvinyl alcohol resin is not particularly limited, for example, be preferably 5 μ m～150 μ m, 10 μ m～100 μ m more preferably.
For above-mentioned polyvinyl alcohol resin film, first implement swelling operation.Swelling operation is within 30 seconds～10 minutes, to carry out by polyvinyl alcohol resin film is flooded in the solution of 20 ℃～50 ℃.Solvent is preferably water.In the situation that shorten the time of manufacturing polarization element, when processing, the dyeing of pigment also can there is swelling, therefore also can omit swelling operation.
After swelling operation, implement dyeing process.Dyeing process is by polyvinyl alcohol resin film immersion is carried out in containing the solution of dichroic dye.Solution temperature in this operation is preferably 5 ℃～60 ℃, more preferably 20 ℃～50 ℃, is particularly preferably 35 ℃～50 ℃.The time being immersed in solution can suitably regulate, preferably according within 30 seconds～20 minutes, regulating, more preferably 1 minute～10 minutes.For colouring method, be preferably immersed in this solution, also can be by this solution coat be carried out on polyvinyl alcohol resin film.
The solution that contains dichroic dye can contain sodium chloride, sodium sulphate, anhydrous sodium sulfate, sodium tripolyphosphate etc. as dyeing assistant.Their content can be adjusted into concentration arbitrarily according to chromatic time, temperature based on dyestuff, as their content separately, is preferably 0～5 % by weight, 0.1 % by weight～2 % by weight more preferably.
After dyeing process, before entering subsequent handling, can carry out matting (hereinafter referred to as matting 1).Matting 1 is the operation of cleaning be attached to the lip-deep dye solvent of polyvinyl alcohol resin film in dyeing process.By carrying out matting 1, can suppress dyestuff transfer to follow-up for the treatment of liquid in.In matting 1, conventionally make water.For cleaning method, preferably impregnated in this solution, also can be by this solution coat be cleaned on polyvinyl alcohol resin film.The time of cleaning is not particularly limited, and is preferably 1 second～300 seconds, more preferably 1 second～60 seconds.Need to can there is not the temperature of dissolving for hydrophilic macromolecule in the temperature of the solvent in matting 1.Conventionally at 5 ℃～40 ℃, carry out cleaning treatment.
After dyeing process or matting 1, the operation that can make polyvinyl alcohol resin film contain crosslinking chemical and/or water-fast agent.As crosslinking chemical, can use boron compounds such as boric acid, borax or ammonium borate; The polyaldehyde such as glyoxal or glutaraldehyde; The multicomponent isocyanate based compound of biuret type, isocyanuric acid ester type or end-sealed type etc.; The titanium sub-group compounds such as titanyl sulfate; Etc., in addition, can also use diglycidyl ether of ethylene glycol, daiamid epoxy chloropropane etc.As water-fast agent, can enumerate succinic acid peroxide, ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether, ammonium chloride or magnesium chloride etc., preferably use boric acid.The operation that the crosslinking chemical that at least one shown in more than using is above and/or water-fast agent make polyvinyl alcohol resin film contain crosslinking chemical and/or water-fast agent.Solvent as now, is preferably water, but is not limited thereto.In the operation that makes polyvinyl alcohol resin film contain crosslinking chemical and/or water-fast agent, for containing for concentration of the crosslinking chemical in solvent and/or water-fast agent, if take boric acid as example, with respect to the concentration of solvent, be preferably 0.1 % by weight～6.0 % by weight, 1.0 % by weight～4.0 % by weight more preferably.Solvent temperature in this operation is preferably 5 ℃～70 ℃, more preferably 5 ℃～50 ℃.For the method that makes polyvinyl alcohol resin film contain crosslinking chemical and/or water-fast agent, preferably impregnated in this solution, also can or smear (Tu work by this solution coat) on polyvinyl alcohol resin film.Processing time in this operation is preferably 30 seconds～and 6 minutes, more preferably 1 minute～5 minutes.But, make polyvinyl alcohol resin film contain crosslinking chemical and/or water-fast agent not necessarily, in the situation that wanting to shorten the time, in the situation that not needing to carry out crosslinking Treatment or resistance to hydration process, can omit this treatment process.
Carrying out dyeing process, matting 1 or making after polyvinyl alcohol resin film contains crosslinking chemical and/or water-fast agent operation, to carry out stretching process.Stretching process is polyvinyl alcohol mesentery to be carried out to the operation of uniaxial tension.Drawing process can be any of wet type pulling method or dry type stretching method.
In the situation of dry type stretching method, in the situation that stretching heating medium body is air dielectric, preferably the temperature at air dielectric is to stretch under ℃ condition of normal temperature～180.In addition, in the atmosphere that is preferably 20%RH～95%RH in humidity, process.As heating means, can enumerate such as region pulling method, roller between roller and add hot-drawing method, pressurization pulling method, infrared heating pulling method etc., but its drawing process is not limited thereto.Stretching process can be 1 section of stretching, also can stretch to carry out by 2 sections of above multistages.
In the situation of wet type pulling method, in water, water-miscible organic solvent or its mixed solution, stretch.Preferably polyvinyl alcohol mesentery is immersed in and in the solution that contains crosslinking chemical and/or water-fast agent, carries out stretch processing simultaneously.As crosslinking chemical, can use boron compounds such as boric acid, borax or ammonium borate; The polyaldehyde such as glyoxal or glutaraldehyde; The multicomponent isocyanate based compound of biuret type, isocyanuric acid ester type or end-sealed type etc.; The titanium sub-group compounds such as titanyl sulfate etc., in addition, can also be used diglycidyl ether of ethylene glycol, daiamid epoxy chloropropane etc.As water-fast agent, can enumerate succinic acid peroxide, ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether, ammonium chloride or magnesium chloride etc.In crosslinking chemical more than containing at least one shown in above and/or the solution of water-fast agent, stretch.Crosslinking chemical is preferably boric acid.For the concentration of the crosslinking chemical in stretching process and/or water-fast agent, for example, be preferably 0.5 % by weight～15 % by weight, 2.0 % by weight～8.0 % by weight more preferably.Stretching ratio is preferably 2 times～8 times, more preferably 5 times～7 times.For draft temperature, preferably at 40 ℃～60 ℃, process, more preferably 45 ℃～58 ℃.Stretching time is generally 30 seconds～and 20 minutes, more preferably 2 minutes～5 minutes.Wet type stretching process can carry out 1 section of stretching, also can stretch to carry out by 2 sections of above multistages.
After having carried out stretching process, because sometimes there is adhering to of separating out of crosslinking chemical and/or water-fast agent or foreign matter on film surface, therefore can carry out the matting (hereinafter referred to as matting 2) that film surface is cleaned.Scavenging period is preferably 1 second～and 5 minutes.Cleaning method is preferably and impregnated in cleaning solution, also can be by by solution coat or be applied on polyvinyl alcohol resin film and clean.Both can carry out 1 section of cleaning treatment, and also can carry out 2 sections of above multistages and process.The solution temperature of matting is not particularly limited, and is generally 5 ℃～50 ℃, is preferably 10 ℃～40 ℃.
As the solvent using in treatment process so far, can enumerate for example water, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE; The alcohols such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, glycerine, ethylene glycol, propylene glycol, diglycol, triethylene glycol, tetraethylene glycol or trimethylolpropane; The amine such as ethylenediamine or diethylentriamine equal solvent, but be not limited to these.In addition, can also use the potpourri of a kind of these above solvent.Most preferred solvent is water.
After stretching process or matting 2, carry out the drying process of film.Dry processing can be undertaken by natural drying, in order further to improve drying efficiency, can or utilize air knife or suction roll etc. carries out surperficial moisture and removes and/or can blow and be dried by the compression based on roller.As dry treatment temperature, preferably at 20 ℃～100 ℃, be dried processing, more preferably at 60 ℃～100 ℃, be dried processing.The dry processing time can be suitable for 30 seconds～and 20 minutes, be preferably 5 minutes～10 minutes.
Further, polarization element of the present invention preferably in the wavelength region may of 500nm≤λ≤560nm transmitance be below 2%.More preferably in the wavelength region may of 540nm≤λ≤550nm, transmitance is below 1%.The blue led of the maximum luminous 440nm of being output as～470nm or blue-fluorescence pipe are attended by faint luminous sometimes near 550nm.In this case, when shading, have light bias and produce, therefore preferably to this luminous control; For the demonstration of this display, the in the situation that in above-mentioned wavelength region may, transmitance 2% being above, tend to obtain sufficient contrast, therefore preferably transmitance is below 2%, more preferably in the wavelength region may of 540nm≤λ≤550nm, transmitance is below 1%.
In addition, in above-mentioned wavelength region may, can there is polarized light property.In this case, preferred Tc≤2% in the wavelength region may of 500nm≤λ≤560nm; More preferably Tc≤1% in the wavelength region may of 540nm≤λ≤550nm.
Their manufacture method is not particularly limited, can enumerate: use the polyvinyl alcohol mesentery in the wavelength region may of 500nm≤λ≤560nm with the dichroic dye of polarized light property to be orientated the film forming, after being coated on the base material film after friction treatment, dichroic dye carried out film or the element of orientation, dichroic dye mixed with liquid-crystalline resin and coat on the base material film after friction treatment after carried out film or the element of orientation, dichroic dye is mixed with liquid-crystalline resin and coat on base material film after by sharing film or the element carried out orientation, make dichroic dye at least in single shaft direction, carry out having carried out on the film after stretch orientation the film of dyeing orientation, make the mixed with resin such as dichroic dye and plastics and at least in single shaft direction, carried out the film of stretch orientation, in addition, can also enumerate following method: by there is film that transmitance is the performance below 2% etc. in the wavelength region may of 500nm≤λ≤560nm, do not have on the polaroid of polarized light property in fitting in the wavelength region may at 500nm≤λ≤560nm.Be preferably and make absorption have the polyvinyl alcohol mesentery of dichroic dye to be orientated the film forming, it does not cause damage to the Tp in the wavelength region may of 420nm≤λ≤490nm.
Use in the situation of dichroic dye as the dichromatism pigment for above-mentioned polarization element, its dichroic dye is not particularly limited, and can enumerate direct direct direct direct direct purple 57, the C.I. directly blue 67 etc. of purple 35, C.I. of purple 9, C.I. of red 81, C.I. of red 79, C.I. such as C.I..These can share with dichroic dye (A) group and/or dichroic dye (B), are not limited to share a kind of, also can share two or more.
The combined amount of these dichroic dyes is not particularly limited, and conventionally with respect to total amount 100 weight portions of dichroic dye (A) group and/or dichroic dye (B), is 25 weight portion～300 weight portions.
In addition, in not hindering the scope of polarized light property, dichroic dye of the present invention can also be used other dichroic dyes.As such dichroic dye, be not particularly limited, can enumerate such as the direct Huang 12 of C.I., the direct Huang 28 of C.I., C.I. Direct Yellow 44 etc.Except the dichroic dye shown in above, can share other organic dyestuff as required.Its blending ratio is not particularly limited.
The use so obtaining the polarization element of dichroic dye be suitable as this display polarization element.
While using iodo-complexes as dichromatism pigment for polarization element of the present invention, preferably Tc (λ 460)≤Tc (λ 600), more preferably Tc (λ 460) < Tc (λ 600).For the polaroid of the known iodo-complexes of use, conventionally in Tc (λ 460) >Tc (λ 600), the scope below wavelength 500nm, cannot obtain high contrast values.In addition, by improving concentration, can obtain high contrast values, but can cause Tp < 30%, cannot obtain sufficient brightness.Based on these reasons, use the polaroid of iodo-complexes to be not suitable as the polaroid for this display.Therefore, use in the situation of iodo-complexes, preferably Tc (λ 460)≤Tc (λ 600).
For using the manufacture method of the polarization element of iodo-complexes and Tc (λ 460)≤Tc (λ 600) not limit, for example, can enumerate and make absorption have the polyvinyl alcohol mesentery of iodo-complexes to be orientated the film forming.
For forming the manufacture method of polyvinyl alcohol resin and the film-forming method of polyvinyl alcohol resin of polarization element, the method described in when using dichroic dye is identical.In addition, the degree of polymerization of polyvinyl alcohol resin is preferably 1,000～10,000, more preferably 1,500～5,000 conventionally.
For above-mentioned polyvinyl alcohol resin film, first implement swelling operation.The method of swelling operation described in when using dichroic dye is identical.
After swelling operation, implement dyeing process.Dyeing process is to utilize the solution that contains iodine and iodide to process polyvinyl alcohol resin film.Solvent as solution is not particularly limited, and is preferably water.As iodide, can enumerate such as iodate alkali metal compounds such as potassium iodides; Ammonium iodide, cobaltous iodide or zinc iodide etc., but be not limited to this, preferably used iodate alkali metal compound, more preferably use potassium iodide.Iodine concentration is preferably 0.0001 % by weight～0.5 % by weight, 0.001 % by weight～0.4 % by weight more preferably.The concentration of iodide is preferably 0.001 % by weight～8 % by weight.Solution temperature in this operation is preferably 5 ℃～50 ℃, more preferably 10 ℃～40 ℃, is particularly preferably 20 ℃～30 ℃.The time impregnated in solution can suitably regulate, preferably according within 30 seconds～6 minutes, regulating, more preferably 1 minute～5 minutes.For colouring method, preferably impregnated in this solution, also can be by by this solution coat or be applied on polyvinyl alcohol resin film and carry out.
While carrying out iodine and iodide processing, in solution, can add crosslinking chemical and/or water-fast agent.Conventionally use crosslinking chemical.As crosslinking chemical, be not particularly limited, be conventionally preferably boric acid.The concentration of for example, adding boric acid is preferably 0.1 % by weight～5.0 % by weight, 2.0 % by weight～4.0 % by weight more preferably.In addition, in the situation that the polyvinyl alcohol resin film that contains iodine, iodide, crosslinking chemical and/or water-fast agent, not necessarily need iodine, iodide, crosslinking chemical and/or water-fast agent directly to contain in polyvinyl alcohol resin film, the form that also comprises reacting contains the situation in film.
In addition, when carrying out dyeing process, can also carry out crosslinking chemical treatment process as mentioned above, but more preferably after dyeing process, carry out crosslinking chemical treatment process.The solution that disposal route now can contain crosslinking chemical by utilization is processed to carry out to the film obtaining in dyeing process.Utilizing this to contain the method that cross-linking agent solution processes and be conventionally preferably the method in this solution by the film immersion after dyeing, can be also coating or the method for smearing this solution on film.This dipping also can carry out before stretching process, in addition, also can carry out together with stretching process.When pulling method is dry type stretching method, preferably before stretching, carry out crosslinking chemical processing; When pulling method is wet type pulling method, preferably carry out together with stretch processing.As crosslinking chemical, identical with the crosslinking chemical described in crosslinking chemical treatment process at dichroic dye.In addition, at this containing the water-fast agent that can coexist in cross-linking agent solution.As water-fast agent, identical with the water-fast agent described in the water-fast agent treatment process of dichroic dye.For the concentration that contains of the crosslinking chemical in solvent, if take boric acid represents as example, with respect to the concentration of solvent, be preferably 0.1 % by weight～6.0 % by weight, 1.0 % by weight～4.0 % by weight more preferably.In this operation, the solvent temperature advancing under market condition at stretching process is preferably 5 ℃～60 ℃, carry out before stretching in the situation that more preferably 5 ℃～40 ℃; While carrying out together with stretching, solvent temperature is more preferably 45 ℃～58 ℃.Processing time in this operation is preferably 30 seconds～and 6 minutes, more preferably 1 minute～5 minutes.
Stretching process has dry type stretching method and wet type pulling method, as the example of its method, identical with the method described in the stretching process of dichroic dye respectively.
After stretch processing, implement to utilize and contain the processing that halid solution carries out.This processing is to adjust color harmony to improve the operation that polarized light property is object.Disposal route is preferably the method in this solution by the film immersion after dyeing, can be also the method that is coated with or smears this solution on film.As halogenide, preference is as iodate alkali metal compounds such as potassium iodide and sodium iodides; The iodide such as ammonium iodide, cobaltous iodide or zinc iodide; The alkali metal chloride such as potassium chloride and sodium chloride compound; Or the chloride such as zinc chloride, be preferably water-soluble.More preferably iodide, more preferably iodate alkali metal compound, be particularly preferably potassium iodide.Halid concentration is the key factor that makes Tc (λ 460)≤Tc (λ 600), its concentration is because of the difference difference of kind, generally, be preferably 6.0 % by weight～15.0 % by weight, more preferably 7.0 % by weight～12.0 % by weight, 8.0 % by weight～10.0 % by weight more preferably.Treatment temperature is also different because of the difference of halid concentration, for example, be preferably 5 ℃～55 ℃, more preferably 20 ℃～40 ℃.Processing time is also different because of the difference of halid concentration, for example, be preferably 1 second～5 minutes; If consider face internal characteristic stable of light polarizing film, be preferably 5 seconds～30 seconds.In addition, by wet type pulling method, undertaken in the situation of stretching process, can also carry out halogenide processing together with stretching process, if but after stretch processing, carry out halogenide processing, stay in grade, therefore preferred.
Solvent as the Treatment Solution in treatment process so far is not particularly limited, and can enumerate such as water, alcohol series solvent or glycol series solvent etc.The water that mixed solvent that in addition, can also use the solution, dimethyl sulfoxide (DMSO) and the water that have mixed water and alcohols etc. is such and the mixed solvent of water-soluble solvent.Most preferably be water.
Halogenide carries out the drying process of film after processing.Method described in the drying method of drying method and dichroic dye is identical.
The use so obtaining the polarization element of iodo-complexes be suitable as this display polarization element.
For resulting polarization element, at its one side or the two-sided protective clear layer that arranges as supporter, thereby form polaroid.For the protective clear layer that the polarization element of the film that polyvinyl alcohol mesentery is orientated form is used, can arrange in the mode of the coating layer based on polymkeric substance or in the mode of the laminated layer of film.In addition, for the protective clear layer for application type polarization element, the base material for coated substrates directly can be arranged to protective clear layer, maybe polarization element can be transferred in to film base material etc. upper and protective seam is set.
As protective clear layer, preferred mechanical intensity is high, the transparent polymer of good thermal stability or film.As the material as protective clear layer, can enumerate for example triacetyl cellulose (TAC), such cellulose acetate resin or its film of diacetyl cellulose; Acrylic resin or its film; Corvic or its film; Vibrin or its film; Polyarylate resin or its film; Cyclic polyolefin resin or its film that the such cyclic olefin of the norborene of take is monomer; Tygon, polypropylene, ring system or there is polyolefin or its multipolymer of norborene skeleton; Main chain or side chain are resin or polymkeric substance or its film of acid imide and/or acid amides; Etc..In addition, as protective clear layer, resin or its film with liquid crystal liquid crystal property can also be set.The thickness of diaphragm is for example 0.5 μ m～200 μ m left and right.By making polaroid at one side or the two-sided same kind in more than 1 layer above-mentioned or variety classes resin or film of arranging.
As the material as protective clear layer, more preferably at least at one side, use PET film.In LCD display in the past, from the viewpoint of the characteristic of LCD and polaroid self, show image, protective clear layer is mainly used the TAC film that height is transparent and birefringence is few.In addition, also sometimes at the one side of protective clear layer, be directly used as phase retardation film of angle of visibility compensate film etc.On the other hand, use in the fluorescence excitation color conversion display of polaroid of the present invention, polaroid act as light switch function, do not need polaroid of the present invention as picture display face.Thus, do not need to use the TAC film of low-birefringence or as the expensive films such as phase retardation film of angle of visibility compensate film, more preferably use the PET film low-cost, mechanical property is excellent and processability is good.The birefringence of PET film is larger, and during therefore as double side support body, transmitance is tended to decline, and is therefore preferably used in the one side of single-side support body or double side support body.In display device, for the configuration of the PET film as polaroid supporter, preferably upper and lower polaroid all relatively polarization element be disposed at the opposition side of liquid crystal layer.In addition, take that to improve transmitance and improve cementability be object, more preferably there is the PET film of easy adhesive linkage.Easy bonding PET film is not particularly limited, and can use commercially available product, more preferably two-sided, is provided with easy adhesive linkage.
The layer that in addition, at least 1 layer of material with the refractive index lower than protective clear layer can be set on protective clear layer is as required as antireflection protective clear layer.By forming antireflection protective seam, thereby the efficiency that sees through of light is improved, can obtain higher contrast value and Tp value.For the material with the refractive index lower than protective clear layer, be not particularly limited, can enumerate the material such as the organic system such as acrylic resin, fluorine-type resin; The inorganic based material such as colloidal silica; Etc., can also share these materials.In addition, can be both reaction system, can be also non-reaction system.Job operation for them is not particularly limited, and can enumerate vapour deposition method, sputtering method, various rubbing methods etc.In addition, as required can also be on protective clear layer lamination multilayer hard conating, high refractive index layer etc.
In above-mentioned, in order to make protective clear layer and polarization element laminating, need cement.As cement, be not particularly limited, preferably polyethylene alcohol is cement.As polyethenol series cement, can enumerate such as Gohsenol NH-26 (the synthetic society of Japan manufactures), Exceval RS-2117 (manufacture of KURARAY society) etc., but be not limited to this.In cement, can add crosslinking chemical and or water-fast agent.In polyethenol series cement, maleic anhydride-isobutylene copolymers can be used, the cement that is mixed with crosslinking chemical can be used as required.As maleic anhydride-isobutylene copolymers, can enumerate such as Isobam#18 (manufacture of KURARAY society), Isobam#04 (manufacture of KURARAY society), ammonia modification Isobam#104 (manufacture of KURARAY society), ammonia modification Isobam#110 (manufacture of KURARAY society), imidizate Isobam#304 (manufacture of KURARAY society), imidizate Isobam#310 (manufacture of KURARAY society) etc.In crosslinking chemical now, can use water-soluble polynary epoxy compound.Water-soluble polynary epoxy compound can be enumerated such as Denacol EX-521 (manufacture of Nagase ChemteX society), Tetrad-C (Mitsui gas chemistry society manufactures) etc.In addition, as the cement beyond polyvinyl alcohol resin, can also use polyurethane series, acrylic acid series, the known like this cement of epoxy system.In addition, take that to improve the bonding force of cement or improve water tolerance be object, can also contain the additives such as zinc compound, chloride, iodide with the concentration of 0.1 % by weight left and right, % by weight～10 simultaneously.For additive, do not limit.After utilizing cement laminating protective clear layer, at suitable temperature, be dried or thermal treatment, thereby obtain polaroid.
In addition, for the laminating of protective clear layer and polarization element can be used bonding agent.As bonding agent, be not particularly limited, as preferred example, can enumerate acrylic adhesive.From aspects such as the characteristics such as bond strength, transmitance and integral thickness, its thickness can be selected arbitrarily, be generally 5 μ m～50 μ m scope, be preferably the scope of 10 μ m～30 μ m.
Polaroid of the present invention can be the polaroid with supporter.In order to attach polaroid, supporter preferably has planar portions, and in addition for for optical applications, supporter is preferably glass ware forming product.As the material of glass, can enumerate the glass such as soda-lime glass (ソ ー ダ ガ ラ ス), pyrex, the inorganic basal disc being formed by crystal, the inorganic systems such as inorganic substrate that formed by sapphire; The plastic plates of the organic system such as acrylic compounds, polycarbonate etc., are preferably the glass of inorganic system.The thickness of glass plate and size can be desired size.In addition, for the polaroid with glass, in order further to improve veneer transmittance, can on its glass surface, be provided with antireflection layer.
In addition, for the laminating of above-mentioned supporter and polarization element or polaroid can be used to cement, bonding agent etc., be not particularly limited, as preferred example, can enumerate acrylic adhesive.From aspects such as the characteristics such as bond strength, transmitance and integral thickness, its thickness can be selected arbitrarily, be generally 5 μ m～50 μ m scope, be preferably the scope of 10 μ m～30 μ m.
The polarization element of the present invention so obtaining and polaroid CR >=8 in Tp >=30% and the wavelength region may between the 20nm of arbitrary continuation in the wavelength region may of 440nm≤λ≤470nm, 000, CR >=5 in all the other wavelength region may, 000, it is suitable as take polarization element and the polaroid being used in the blue led of the luminous 440nm of the being output as～470nm of maximum or fluorescence excitation color conversion display that blue-fluorescence pipe is light source.
Embodiment
Illustrate in greater detail by the following examples the present invention, but the present invention is not limited to these embodiment.It should be noted that, the evaluation of the transmitance shown in embodiment is carried out according to the following stated method.
While using spectrophotometer (Japan Spectroscopy Corporation manufactures " V-7100 ") to measure transmitance, in the exiting side of light, based on JIS-Z8701 (2 ° of visuals field of illuminant-C), make the illuminant-C light of the transmitance 100% after visibility is proofreaied and correct can incide mensuration sample.
To 2 polaroid incident illuminant-C light of the present invention, the parallel mode of absorption axes direction according to 2 polaroids is measured to parallel (parallel Nicol) spectrophotometric transmittance obtaining and be made as Tp; The mode of the absorption axes direction quadrature according to 2 polaroids is measured to quadrature (cross Nicols) spectrophotometric transmittance obtaining and be made as Tc.In addition, contrast is the contrast based on spectrophotometric transmittance, is expressed as the value consisting of CR=Tp/Tc.
Transmitance is separately by being used spectrophotometer (Japan Spectroscopy Corporation manufactures " V-7100 ") to measure.
Embodiment 1
The polyvinyl alcohol resin film (KURARAY society manufactures VF series) that is more than 99% thickness 75 μ m by saponification degree floods and within 3 minutes, carries out swelling treatment in the warm water of 40 ℃.Using the film immersion that has carried out swelling treatment in contain 0.04 % by weight as C.I. direct orange 39, the 0.1 % by weight sodium tripolyphosphate of pigment of dichroic dye (A) group, in the aqueous solution of 45 ℃ of 0.1 % by weight saltcake, carry out the dyeing of pigment and process, pigment is adsorbed on polyvinyl alcohol mesentery.Water has the film of pigment to clean to absorption, after cleaning, utilizes the aqueous solution of 40 ℃ of the boric acid that contains 2 % by weight to carry out boric acid processing in 1 minute.The film obtaining after on one side boric acid being processed is stretched to 5.0 times, in the aqueous solution of contain boric acid 3 % by weight 55 ℃ carry out 5 minute processing on one side.The film obtaining after this boric acid is processed keeps tense situation, utilizes the water of normal temperature to carry out processing for 15 seconds simultaneously.The film obtaining after processing is carried out to 9 minutes dry processing at 70 ℃ at once, thereby obtain the polarization element of thickness 25 μ m.For resulting polarization element, use is provided with the acrylic adhesive of PET film (Toyo Boseki K.K manufactures Cosmoshine A4300), polyethenol series cement and the thickness 20 μ m of the thickness 100 μ m of two-sided easy adhesive linkage, according to carrying out lamination on the such glass substrate that is formed in thickness 1mm of PET/ adhesive linkage/polarization element/bonding coat/glass, thereby carry out lamination, obtain polaroid, as measuring sample.
Embodiment 2
As the pigment being adsorbed, using the dichroic dye (B) of 0.02 % by weight is the pigment shown in formula (1), in formula (1), and R
1, R
2for hydrogen atom, the ratio of the n being measured by HPLC is: n=1 is 33%, n=2 is 65%, n=3 is 2%, in addition, makes similarly to Example 1 polaroid, as measuring sample.
Embodiment 3
As the pigment being adsorbed, use the C.I. direct orange 39 of pigment as dichroic dye (A) group of 0.018 % by weight and the pigment shown in the formula as dichroic dye (B) of 0.015 % by weight (1), in formula (1), R
1, R
2for hydrogen atom, the ratio of the n being measured by HPLC is: n=1 is 33%, n=2 is 65%, n=3 is 2%, in addition, makes similarly to Example 1 polaroid, as measuring sample.
Embodiment 4
As the pigment being adsorbed, the C.I. that uses the pigment shown in the formula as dichroic dye (B) (1) of C.I. direct orange 39,0.01 % by weight of the pigment as dichroic dye (A) group of 0.01 % by weight and 0.02 % by weight directly red 81, in formula (1), R
1, R
2for hydrogen atom, the ratio of the n being measured by HPLC is: n=1 is 33%, n=2 is 65%, n=3 is 2%, in addition, makes similarly to Example 1 polaroid, as measuring sample.
Embodiment 5
The polyvinyl alcohol resin film (KURARAY society manufactures VF series) that is more than 99% thickness 75 μ m by saponification degree floods and within 3 minutes, carries out swelling treatment in the warm water of 40 ℃.By the film immersion that the has carried out swelling treatment processing of dyeing in the aqueous solution of 30 ℃ that contains boric acid 2.8 % by weight, iodine 0.044 % by weight, potassium iodide 3.13 % by weight, pigment is adsorbed on polyvinyl alcohol mesentery.The film that has carried out pigment dyeing is stretched to 5.0 times on one side, in the aqueous solution of contain boric acid 3.0 % by weight 50 ℃ carry out 5 minute processing on one side.The film obtaining after this boric acid is processed keeps tense situation, carries out 20 seconds complementary colors simultaneously and process in the aqueous solution of 30 ℃ that contain potassium iodide 8.0 % by weight.The film obtaining after processing is carried out to 9 minutes dry processing at 70 ℃ at once, thereby obtain the polarization element of thickness 25 μ m.Use be provided with the thickness 100 μ m of two-sided easy adhesive linkage PET film (Toyo Boseki K.K manufacture Cosmoshine A4300), polyethenol series cement and thickness 20 μ m acrylic adhesive by resulting polarization element according to the such formation lamination of PET/ adhesive linkage/polarization element/bonding coat/glass on the glass substrate of thickness 1mm, thereby carry out lamination, obtain polaroid, as measuring sample.
Comparative example 1
The acrylic adhesive of used thickness 20 μ m takes out the liquid crystal TV set from commercially available (Sharp Corporation manufactures AQUOS/32 inch), protective clear layer is that the iodine of two-sided TAC film is that polaroid fits in the glass substrate of thickness 1mm, as measuring sample.
Comparative example 2
The aqueous solution of 30 ℃ that utilization contains potassium iodide 5.0 % by weight is carried out complementary color processing in 20 seconds, in addition, makes similarly to Example 4 polaroid, as measuring sample.
The Tp of spectral photometry value that the mensuration sample being obtained by embodiment 1～5 and comparative example 1～2 is measured to each wavelength of the unit distance 5nm obtaining is shown in Fig. 1, and its Tc is shown in Fig. 2.In 420nm～490nm, the Tp of each wavelength is shown in Table 4, its contrast value is shown in Table 5, the Tc of each wavelength is shown in Table 6 in 500nm～560nm.In addition, in table 7, having illustrated as iodine is the value of the embodiment 4 of polaroid 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 4 | 0.0018 | 0.0080 |
| Comparative example 1 | 0.0062 | 0.0018 |
| Comparative example 2 | 0.0046 | 0.0015 |
Known according to the result of Fig. 1～2 and table 4～5: for the use of embodiment 1～4 polaroid of dichroic dye, in the wavelength region may of 420nm～490nm, Tp is higher, contrast is higher, particularly excellent in the wavelength region may of 440nm～470nm.Further, known according to table 6: embodiment 4 is in the wavelength region may of 500nm～560nm, and Tc is lower.Known: wherein the band territory of the high-contrast of embodiment 3 and 4 the polaroid that share dichroic dye (A) and dichroic dye (B) is wider, very excellent in the wavelength region may of 440nm～470nm.In addition, iodine for embodiment 5 is polaroid, according to the known Tc of table 7 (460)≤Tc (600), although the use of embodiment 1～3 polaroid of dichroic dye poor, but in the wavelength region may of 440nm～470nm, obtained the result that Tp is higher, contrast is higher.
On the other hand, for the known common iodine of comparative example 1～2 is polaroid, according to the known Tc of table 7 (460) >Tc (600), known according to the result of Fig. 1～2 and table 4～5: its result is that in wavelength region may, the particularly wavelength region may below 460nm at 420nm～490nm, Tp is lower, contrast is also insufficient.
Industrial applicibility
Polarization element of the present invention and polaroid are excellent at the polarized light property of the wavelength region may of 440nm≤λ≤470nm, and it can be as take the blue led of the luminous 440nm of the being output as～470nm of maximum or polarization element and the polaroid of the fluorescence excitation color conversion display that blue-fluorescence pipe is light source.
Claims (9)
1. a polarization element, it is for take the blue led of the luminous 440nm of the being output as～470nm of maximum or the fluorescence excitation color conversion display that blue-fluorescence pipe is light source, this polarization element is characterised in that, Tp >=30% in the wavelength region may of 440nm≤λ≤470nm, and CR >=8 in the wavelength region may between the 20nm of the arbitrary continuation in this wavelength region may, 000, CR >=5 in remaining wavelength region may, 000, and at least contain dichromatism pigment
Wherein, λ represents wavelength; Tp refers to the spectrophotometric transmittance (transmitance during parallel Nicol) when 2 polarization elements are overlapping according to the parallel mode of its absorption axes separately; Tc refers to the spectrophotometric transmittance (transmitance during cross Nicols) when 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately; CR is the abbreviation of contrast, and it represents the value consisting of Tp/Tc.
2. polarization element as claimed in claim 1, is characterized in that, in the wavelength region may of 420nm≤λ < 440nm, and Tp >=30% and CR >=1,500.
3. polarization element as claimed in claim 1 or 2, is characterized in that, in the wavelength region may of 470nm < λ≤490nm, and Tp >=30% and CR >=1,000.
4. the polarization element as described in claim 1～3 any one, wherein, dichromatism pigment at least contains a kind of in dichroic dye (A) group and/or dichroic dye (B) that formula (1) is represented,
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, R
1, R
2represent independently of one another hydrogen atom, low alkyl group, lower alkoxy; N represents n=1～3.
5. the polarization element as described in claim 1～4 any one, is characterized in that, in the wavelength region may of 500nm≤λ≤560nm, transmitance is below 2%.
6. the polarization element as described in claim 1～3 any one, is characterized in that, dichromatism pigment is iodo-complexes, and Tc (λ 460)≤Tc (λ 600),
The spectrophotometric transmittance at 460nm place of (during cross Nicols) when herein, Tc (λ 460) is that 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately; The spectrophotometric transmittance at 600nm place of (during cross Nicols) when Tc (λ 600) is that 2 polarization elements are overlapping according to the mode of its absorption axes quadrature separately.
7. the polaroid as described in any one of claim 1～6, wherein, this polaroid is to form by support film being set at least one side of polarization element.
8. polaroid as claimed in claim 7, wherein, at least one side of support film is PET (polyester) film.
9. with a polaroid for inorganic substrate, it is characterized in that have the right polarization element described in requirement 1～6 any one or the polaroid described in claim 7 or 8 of lamination on inorganic substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-160622 | 2011-07-22 | ||
| JP2011160622 | 2011-07-22 | ||
| PCT/JP2012/067892 WO2013015134A1 (en) | 2011-07-22 | 2012-07-13 | Polarization element and polarization plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103649793A true CN103649793A (en) | 2014-03-19 |
| CN103649793B CN103649793B (en) | 2017-07-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280035152.4A Expired - Fee Related CN103649793B (en) | 2011-07-22 | 2012-07-13 | Polarization element and polarizer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6006210B2 (en) |
| KR (1) | KR101918543B1 (en) |
| CN (1) | CN103649793B (en) |
| TW (1) | TWI582472B (en) |
| WO (1) | WO2013015134A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106967308A (en) * | 2015-11-06 | 2017-07-21 | 日本化药株式会社 | Polarization element, Polarizer and liquid crystal display device |
| WO2019006795A1 (en) * | 2017-07-06 | 2019-01-10 | 深圳市华星光电技术有限公司 | Liquid crystal panel, liquid crystal display, and method for manufacturing yellow dye polarizer |
| CN110832363A (en) * | 2017-07-28 | 2020-02-21 | 日本化药株式会社 | Polarized light emitting element, polarized light emitting panel, display device, and method for manufacturing polarized light emitting element |
| 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 |
| CN111356946A (en) * | 2017-11-06 | 2020-06-30 | 日本宝来科技有限公司 | Polarizing element and head-up display device provided with same |
| CN111433290A (en) * | 2017-12-22 | 2020-07-17 | 日本化药株式会社 | Azo compound or salt thereof, and polarizing element, polarizing plate and display device each containing the same |
| US11802208B2 (en) | 2017-07-28 | 2023-10-31 | Nippon Kayaku Kabushiki Kaisha | Stilbene-based compound or salt thereof, and polarizing film, polarizing plate, and display device |
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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 |
| CN110366691B (en) | 2017-03-03 | 2022-02-18 | 日本化药株式会社 | Image display device |
| JP2019056904A (en) * | 2017-09-20 | 2019-04-11 | 日本化薬株式会社 | Plane polarized light emitting element |
| 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 |
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- 2012-07-13 WO PCT/JP2012/067892 patent/WO2013015134A1/en active Application Filing
- 2012-07-13 KR KR1020137032915A patent/KR101918543B1/en active IP Right Grant
- 2012-07-13 JP JP2013525664A patent/JP6006210B2/en not_active Expired - Fee Related
- 2012-07-13 CN CN201280035152.4A patent/CN103649793B/en not_active Expired - Fee Related
- 2012-07-13 TW TW101125456A patent/TWI582472B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106967308A (en) * | 2015-11-06 | 2017-07-21 | 日本化药株式会社 | Polarization element, Polarizer and liquid crystal display device |
| CN106967308B (en) * | 2015-11-06 | 2020-06-26 | 日本化药株式会社 | Polarizing element, polarizing plate and liquid crystal display device |
| WO2019006795A1 (en) * | 2017-07-06 | 2019-01-10 | 深圳市华星光电技术有限公司 | Liquid crystal panel, liquid crystal display, and method for manufacturing yellow dye polarizer |
| 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 |
| CN110832363A (en) * | 2017-07-28 | 2020-02-21 | 日本化药株式会社 | Polarized light emitting element, polarized light emitting panel, display device, and method for manufacturing polarized light emitting element |
| CN110832363B (en) * | 2017-07-28 | 2022-07-22 | 日本化药株式会社 | Polarized light emitting element, polarized light emitting panel, display device, and method for manufacturing polarized light emitting element |
| US11802208B2 (en) | 2017-07-28 | 2023-10-31 | Nippon Kayaku Kabushiki Kaisha | Stilbene-based compound or salt thereof, and polarizing film, polarizing plate, and display device |
| CN111356946A (en) * | 2017-11-06 | 2020-06-30 | 日本宝来科技有限公司 | Polarizing element and head-up display device provided with same |
| CN111433290A (en) * | 2017-12-22 | 2020-07-17 | 日本化药株式会社 | Azo compound or salt thereof, and polarizing element, polarizing plate and display device each containing the same |
| CN111433290B (en) * | 2017-12-22 | 2022-06-14 | 日本化药株式会社 | Azo compound or salt thereof, and polarizing element, polarizing plate and display device each comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201312174A (en) | 2013-03-16 |
| WO2013015134A1 (en) | 2013-01-31 |
| TWI582472B (en) | 2017-05-11 |
| CN103649793B (en) | 2017-07-21 |
| JPWO2013015134A1 (en) | 2015-02-23 |
| JP6006210B2 (en) | 2016-10-12 |
| KR20140068805A (en) | 2014-06-09 |
| KR101918543B1 (en) | 2018-11-14 |
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