CN105899979B - The polarizer and polarizer of the high contrast with uniform transmissivity under each wavelength - Google Patents
The polarizer and polarizer of the high contrast with uniform transmissivity under each wavelength Download PDFInfo
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- CN105899979B CN105899979B CN201480063578.XA CN201480063578A CN105899979B CN 105899979 B CN105899979 B CN 105899979B CN 201480063578 A CN201480063578 A CN 201480063578A CN 105899979 B CN105899979 B CN 105899979B
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0011—Monoazo dyes prepared by diazotising and coupling from diazotized anilines from diazotized anilines directly substituted by a heterocyclic ring (not condensed)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
Abstract
The problem of the present invention is to provide a kind of polarizer and polarizer, the polarizer of the application is in the case of by absorption axiss configured in parallel and in the case of orthogonal configuration, there is the transmissivity of constant in terms of each Thewavelengthtransmittance in every case, and with high contrast.The solution of the present invention is a kind of polarizer, it is formed it includes the hydrophilic macromolecule by absorption boric acid and drawn and the base material with polarization function containing iodine, the polarizer is characterized in that, contained in the form of free acid organic compound represented by formula (1) or its salt (in formula (1), R1Represent that hydrogen atom, halogen atom, low alkyl group, lower alkoxy or carboxyl, k, m, n represent 0 or 1 respectively.Wherein, m+n>1.), the visibility when base material is measured using monolithic corrects single plate transmission Yc as 40.0%~42.5%, the single plate transmission Ts of visibility correction single plate transmission Ys and 460nm460Difference within 1.2%, the single plate transmission Ts of visibility correction single plate transmission Ys and 550nm550Difference within 1%, the single plate transmission Ts of visibility correction single plate transmission Ys and 610nm610Difference within 1%, visibility correction of orthogonal transmissivity when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials is less than 0.01%, and the average value Tc Ave430 480 of the orthogonal transmission of 430nm~480nm when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials are less than 0.03%.
Description
Technical field
The present invention relates to the polarizers and polarizer with uniform transmissivity and with high contrast under each wavelength.
Background technology
Polarizer is typically to be adsorbed by the iodine or dichroic dye for making to be used as dichroism pigment in polyvinyl alcohol resin
On film and it is orientated what is manufactured.It is bonded on at least single side of the polarizer by adhesive layer by triacetyl cellulose
It waits the protective film of formation and polarizer is made, in liquid crystal display device etc..Using iodine as the polarizer of dichroism pigment
It is referred to as iodine system polarizer, on the other hand, it is inclined that the polarizer using dichroic dye as dichroism pigment is referred to as dyestuff system
Shake piece.Wherein, dyestuff system polarizer possesses with high-fire resistance, high wet heat durability, high stability and is obtained by mixture
Color high selectivity as feature, on the other hand, compared with the iodine system polarizer with identical degree of polarization, there is transmission
The problem of rate is low, i.e. contrast is low such.Polarizer so far shows white absorption axiss are set in parallel
When, the transmissivity of 380nm~480nm is less than the transmissivity of 500nm~600nm, cannot keep the uniformity of luminance under each wavelength.
Therefore, following trial has been carried out：Such as in the case where the absorption axiss of polarizer are set in parallel, to each Thewavelengthtransmittance
Improved with constant transmissivity.But there is also following problems in this case：Absorption axiss are being arranged to normal axis
When, the transmissivity near the wavelength 550nm higher than visibility of the wavelength of 380nm~480nm, particularly 460nm is high, contrast
It reduces.Therefore, as polarizer or polarizer, it is desirable that can also make while with high polarization property, i.e. high contrast
Each Thewavelengthtransmittance of visibility region constant polarizer or polarizer.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-49698
Patent document 2：Japanese Unexamined Patent Publication 2005-202367
Non-patent literature 1：Machine energy property pigment ying (functional pigmented application) the 1st printing release, strain formula meeting
Society CMC is published, and is entered Jiang Zhenghao and is edited, page 98~100
The content of the invention
Problems to be solved by the invention
Such as the side for making the transmissivity of polarizer constant under each wavelength is disclosed in patent document 1 or patent document 2
Method.The transmissivity during cross Nicols of 410nm in the polarizer for being 8 μm~18 μm in film thickness is disclosed in patent document 1
For the technology of 0.001%~0.1% polarizer.But the technology only improves colour fading and the tone of the orthogonal positions of 410nm, and
Do not improve each Thewavelengthtransmittance during parallel position, in addition, in recent years be provided with liquid crystal of the LED light source as backlight
In showing device, almost complete absence of 410nm shine, for blue-light-emitting, using 460nm as the 430nm of bright line~
480nm is main illuminating source, therefore the contrast of 410nm is substantially not required.Therefore, in order to improve contrast, it is necessary to
Improve the contrast of the wavelength of 430nm~480nm.In the case of the formula of patent document 1, parallel position can not be fully obtained
Tone improves, and when for having used in display device of the LED light source when backlights, can not fully obtain contrast.Specially
A kind of technology of the polarizer formed by film is disclosed in sharp document 2, which has sets by the water solubility containing divalent metal
The structure of tiny area is dispersed in the matrix that fat is formed.But parallel position and orthogonal position can not be also obtained using the technology
The transmissivity of each wavelength constant polarizer or polarizer.
Means for solving the problems
The present inventor conducts in-depth research to solve the above subject, as a result completes the present invention.
That is, the present invention relates to：
" a kind of (1) polarizer is formed and contained it includes the hydrophilic macromolecule by absorption boric acid and drawn
The base material with polarization function of iodine, the polarizer be characterized in that,
Contain the organic compound or its salt represented by formula (1) in the form of free acid,
[changing 1]
(in formula (1), R1Represent that hydrogen atom, halogen atom, low alkyl group, lower alkoxy or carboxyl, k, m, n represent 0 respectively
Or 1.Wherein, m+n>1.)
The visibility when base material is measured using monolithic corrects single plate transmission Yc as 40.0%~42.5%,
The single plate transmission Ts of visibility correction single plate transmission Ys and 460nm460Difference within 1.2%,
The single plate transmission Ts of visibility correction single plate transmission Ys and 550nm550Difference within 1%,
The single plate transmission Ts of visibility correction single plate transmission Ys and 610nm610Difference within 1%,
Visibility correction of orthogonal when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials is saturating
It is less than 0.01% to penetrate rate,
430nm~480nm when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials is just
The average value Tc Ave430-480 for handing over transmissivity are less than 0.03%；
(2) polarizer as described in above-mentioned (1), which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 above-mentioned base materials being made parallelly to be measured to 2 above-mentioned base materials is flat
Row transmissivity Yp is 33%~37% scope,
The parallel transmission Yp of the substrate and make 2 base materials compared with absorb direction of principal axis parallelly to 2 base materials into
The transmissivity Tp of 255nm when row measures255Meet following formula (2)：
0.75×Yp-13≤Tp255≤ 0.75 × Yp+1.0 formulas (2)；
(3) polarizer as described in above-mentioned (1) or (2), which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 above-mentioned base materials being made parallelly to be measured to 2 above-mentioned base materials is flat
Row transmissivity Yp is 33%~37% scope,
Parallel transmission Yp and when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials
The transmissivity Tc of 255nm255Meet following formula (3)：
2.0×10-6×Yp4.1≤Tc255≤2.0×10-6×Yp4.4Formula (3)；
(4) polarizer as any one of above-mentioned (1)~(3), which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 above-mentioned base materials being made parallelly to be measured to 2 above-mentioned base materials is flat
Row transmissivity Yp is 33%~37% scope,
Parallel transmission Yp is with making the absorption direction of principal axis of 2 above-mentioned base materials be parallelly measured to 2 above-mentioned base materials
When 460nm parallel transmission Tp460Difference within 3%；
(5) polarizer as any one of above-mentioned (1)~(4), which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 above-mentioned base materials being made parallelly to be measured to 2 above-mentioned base materials is saturating
The scope that rate Yp is 33%~37% is penetrated,
Parallel transmission Yp is with making the absorption direction of principal axis of 2 above-mentioned base materials be parallelly measured to 2 above-mentioned base materials
When 295nm transmissivity Tp295Meet following formula (4),
Parallel transmission Yp is with making the absorption direction of principal axis of 2 above-mentioned base materials be parallelly measured to 2 above-mentioned base materials
When 360nm transmissivity Tp360Meet following formula (5)：
1.05×Yp-26≤Tp295≤ 1.05 × Yp-13 formulas (4)
1.25×Yp-26.25≤Tp360≤ 1.25 × Yp-16.25 formulas (5)；
(6) polarizer as any one of above-mentioned (1)~(5), which is characterized in that
The transmissivity of 295nm when the absorption direction of principal axis of 2 above-mentioned base materials being made orthogonally to be measured to 2 above-mentioned base materials
Tc295Meet formula (6), also,
The transmissivity Tc of 360nm when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials360
Meet formula (7)：
2.0×10-30×Yp18.6≤Tc295≤2.0×10-30×Yp19.4Formula (6)
4.0×10-37×Yp22.12≤Tc360≤4.0×10-37×Yp22.67Formula (7)；
(7) polarizer as any one of above-mentioned (1)~(6), which is characterized in that
The transmissivity of 460nm when the absorption direction of principal axis of 2 above-mentioned base materials being made orthogonally to be measured to 2 above-mentioned base materials
Tc460For less than 0.035%, also,
The transmissivity Tc of 610nm when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials610
For less than 0.01%；
(8) polarizer as any one of above-mentioned (1)~(7), which is characterized in that
Above-mentioned base material is made of polyvinyl alcohol resin film,
The degree of polymerization of the polyvinyl alcohol resin film is 3000~7000；
(9) a kind of polarizer is at least single side setting in the polarizer any one of above-mentioned (1)~(8)
What support film formed；
(10) a kind of liquid crystal display device possesses the polarizer or above-mentioned any one of above-mentioned (1)~(8)
(9) polarizer described in；
(11) a kind of manufacturing method of polarizer, the polarizer include high by the hydrophily of absorption boric acid and drawn
Molecule is formed and the base material with polarization function containing iodine, the manufacturing method are characterized in that,
Including following processes：
(i) process for obtaining the film containing dichroism pigment in polyvinyl alcohol resin film containing dichroism pigment is made；
(ii) process that the above-mentioned film containing dichroism pigment is stretched into the film for obtaining drawn；
(iii) work that the solution using chloride or the solution containing iodide post-process the film of above-mentioned drawn
Sequence；With
(iv) make film dry after above-mentioned post processing and obtain the process of above-mentioned base material,
The concentration of the solution of above-mentioned chloride or solution containing iodide is the weight % of 0.1 weight %~15,
The process that the manufacturing method further comprises making the organic compound containing following formula (1) in base material,
[changing 2]
The effect of invention
The present invention relates to the polarizers and polarization with constant transmissivity and with high contrast under each wavelength
Piece, the polarizer and polarizer can be used as transmissivity height, contrast ratio high and the very high display of color reprodubility is used
Polarizer, particularly liquid crystal display are used with polarizer.Having used the display of the polarizer and polarizer that can become can
By property it is high, for a long time for high contrast and the display with high color reprodubility.
Specific embodiment
<Polarizer>
As the method for the polarizer for making the present invention, for example, following methods：Into enforcement hydrophily high score
The process of sub- membrane swelling followed by the dyeing process that it is made to contain dichroism pigment, next carries out water-fast as needed
Change treatment process, subsequent pass through stretching process, subsequent pass through postprocessing working procedures, finally made by drying process.
As the hydrophilic macromolecule film used in polarizer, for example, by polyvinyl alcohol resin, straight chain
The film of the compositions such as starch-series resin, starch-series resin, cellulose-based resin or polyacrylate system resin, using pass through pour into a mould etc.
By these resins be made it is membranaceous obtained by material.Wherein, preferred polyvinyl alcohol resin (being also referred to as sometimes below " PVA ")
Film.In the present invention, the dichroic substances structure such as polyvinyl alcohol resin film and iodine for being most preferably made of polyvinyl alcohol resin
Into polarizer.The thickness of these polarizers is not particularly limited, generally 5 μm~80 μm or so.
The manufacturing method of above-mentioned polyvinyl alcohol resin is not particularly limited, and can be made using well known method.Example
Such as, polyvinyl alcohol resin can be obtained by the way that polyvinyl acetate system resin is carried out saponification.Herein, as poly- acetic acid second
Enester system resin in addition to as the polyvinyl acetate of the homopolymer of vinyl acetate, can also enumerate vinyl acetate
With the copolymer of other monomers that can be copolymerized with it etc..As such as being lifted with the other monomers of vinyl acetate copolymerization
Go out unsaturated carboxylic acid class, olefines, vinyl ethers or unsaturated sulfonic acid class etc..The polyvinyl alcohol resin can further into
It has gone modification, such as polyvinyl formal, polyvinyl acetal being modified with aldehydes etc. can also be used.Separately
Outside, the degree of polymerization of polyvinyl alcohol resin is preferably generally 1,000~10,000, more preferably 1,500~6,000.By poly- second
Material obtained by enol system resin film forming is used as polyvinyl alcohol resin film.
In order to improve the optical characteristics of the present invention, the degree of polymerization of PVA need for 1000~10000, more preferably 3000 with
On.If the degree of polymerization of PVA is less than 2000, it is difficult to show high polarization property.If the degree of polymerization is hardened more than 7000, PVA, into
Film, draftability reduce, and productivity reduces, thus are preferably less than 10000 from the aspect of industry.
The degree of polymerization of PVA refers to the degree of polymerization measured as follows (viscometric degree of polymerization).
With distilled water 70g in 95 DEG C of dissolving PVA 0.28g, 0.4%PVA aqueous solutions are made, are cooled to 30 DEG C.At 30 DEG C
It is cooled down in Water Tank with Temp.-controlled, polymerization degree measurement sample is made.Next, by polymerization degree measurement sample in evaporating dish
When 10mL is small with 105 DEG C of drying machine drying 20, weight [α (g)] after the drying of polymerization degree measurement sample is measured.The degree of polymerization is surveyed
Surely the concentration C (g/L) of sample is used to be calculated by following formula (i).
The formula (i) of C=1000 × α/10
And then polymerization degree measurement sample or distilled water are put into Ostwald viscometer with 10mL full doses pipette
In, stablize in 30 DEG C of Water Tank with Temp.-controlled 15 minutes.Measure the outflow number of seconds t of input polymerization degree measurement sample1(second)
With the outflow number of seconds t of distilled water0(second) calculates viscometric degree of polymerization E by following formula (ii)~formula (iv).
η t=t1/t0Formula (ii)
η=2.303 × Log (η t/c) formula (iii)
Log (E)=1.613 × Log ([η] × 104/8.29) formula (iv)
The saponification degree of PVA is preferably 99 moles of more than %, more preferably 99.5 moles of more than %.If saponification degree rubs less than 99
You are %, then PVA is easily dissolved out, it is possible to which inducing dyeability uneven, in dyeing process in the face of optical characteristics reduces, stretches work
Cut-out in sequence and significantly reduce productivity, therefore not preferably.
The PVA used in the present invention polyvinylesters based polymer can be carried out as obtained from polymerizeing vinyl esters
Saponification manufactures.As vinyl esters, can exemplify vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate,
New vinyl acetate acid, vinyl neodecanoate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate etc., from wherein selecting
It is one kind or two or more.Wherein it is preferable to use vinyl acetates.Polymerization temperature is not particularly limited, and is using methanol molten as polymerizeing
In the case of agent, since the boiling point of methanol is near 60 DEG C, thus preferably 60 DEG C or so.As long as the effect of the present invention is not damaged
Fruit, then PVA be not limited to the saponified of the homopolymer of vinyl esters.For example, it is also possible to be less than 5 moles of % in PVA
Ratio graft copolymerization unsaturated carboxylic acid or derivatives thereof, unsaturated sulfonic acid or derivatives thereof, α-alkene that carbon number is 2~30
Modified PVA l vinyl esters that hydrocarbon etc. forms and to be less than ratio copolymerization unsaturated carboxylic acid of 15 moles of % or derivatives thereof, no
The modified poly ethylene base ester that saturation sulfonic acid or derivatives thereof, alpha-olefin etc. that carbon number is 2~30 form it is saponified；It utilizes
The aldehydes such as formaldehyde, butyraldehyde, benzaldehyde make a part of hydroxyl of PVA be crosslinked Pioloform, polyvinyl acetal based polymer formed etc..
By the way that the PVA obtained as described above is formed a film, base film can be obtained.As the film build method of PVA, except will be aqueous
Beyond the method for PVA melting extrusions, casting filming therapy, wet type membrane formation (being discharged in poor solvent), gel can also be enumerated
PVA aqueous solutions (are flow to base by membrane formation process (by PVA aqueous solutions elder generation cooling gel, then extraction removes solvent), cast membrane formation process
It is on disk and dry) and method based on combination thereof etc., but it is not limited to these methods.
The solvent used during as film forming, for example, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide
Amine, N-Methyl pyrrolidone, ethylene glycol, glycerine, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane,
Ethylenediamine, diethylenetriamines, water etc., but it is not limited to these.Solvent can be a kind, can also mix two or more to make
With.The amount of the solvent used during film forming is, for example, the mass % of 50 mass %~95, be preferably 70 mass %~95 mass %, but not
It is defined in these scopes.But if the amount of solvent is less than 50 mass %, the viscosity of the stoste that forms a film raises, when preparation, was difficult to
Filter, deaeration, it is difficult to obtain without foreign matter and not have defective base film.In addition, if volatile ingredient rate is more than 95 mass %, form a film
The viscosity of stoste becomes too low, it is difficult to the control of target thickness is carried out, it is dry because wind when drying generates the influence rocked on surface
Time is elongated, and productivity reduces.
When manufacturing base film, plasticizer can be used.As plasticizer, glycerine, diglycerol, ethylene glycol etc. can be enumerated,
But it is not limited to these.The dosage of plasticizer is it is not also specifically limited, it is preferably 5 mass to be commonly angled relative to 100 mass parts of PVA
Part~15 in the range of mass parts.
As the drying means of the base film after film forming, for example, utilizing the drying of hot wind, the contact using hot-rolling
It dries, using drying of infrared heater etc., but does not limit.Can be individually using one kind in these methods, it can also
Two or more combinations are dried.To drying temperature it is not also specifically limited, in the range of preferably 50 DEG C~70 DEG C.
For dried base film, in order to control its swellbility in aftermentioned prescribed limit, preferably it is heat-treated.Make
For the heat treatment method of the base film after film forming, for example, using the method for hot wind, the method that base film is made to be contacted with hot-rolling,
As long as can using the method that is handled of heat as long as be not particularly limited.One kind in these methods can be individually used,
It can be combined two or more.Heat treatment temperature and time are not particularly limited, are preferably 110 DEG C~140 DEG C of model
In enclosing, the processing of substantially 1 minute~10 minutes is appropriate, but is not particularly limited.
The thickness of so obtained base film is preferably 20 μm~100 μm, it is 20 μm~80 μm more preferable, further preferably 20
μm~60 μm.If thickness is less than 20 μm, the fracture of film easily occurs.If thickness more than 100 μm, applies film when stretching
Stress becomes larger, and the mechanical load in stretching process becomes larger, it is necessary to for can tolerate the large-scale device of the load.
The swellbility F of base film is preferably 180%~250%, is more preferably 205%~235%, further preferably
210%~230%.If swellbility F is less than 180%, elongation when stretching is small, the possibility liter being broken in low range
It is high, it is difficult to sufficiently to be stretched.In addition, if swellbility F is more than 240%, swelling becomes excessive, can generate fold and pine
It relaxes, cut-out when causing to stretch.In order to control swellbility F, such as can be using when being heat-treated to the base film after film forming
Temperature and time reaches suitable swellbility F.
The assay method of the swellbility F of base film is as follows.
Base film is cut into 5cm × 5cm, when dipping 4 is small in 30 DEG C of 1 liter of distilled water.Film after this is impregnated is from steaming
It is taken out in distilled water, after clipping the water droplet of sorbent surface with two filter paper, measures the weight [β (g)] of the film after being impregnated into water.Into
And will impregnate and absorb the film of water droplet it is small with 105 DEG C of drying machine drying 20 when, after cool down 30 minutes in drier, survey
The weight [γ (g)] of fixed dried film calculates the swellbility F of base film by formula (v).
Swellbility F=100 × β/γ (%) formula (v)
Using the base film made as described above, the inclined of the present invention is manufactured by including the method for process described below
Shake element.
(swelling process)
First, above-mentioned base film is supplied to makes the swelling process of membrane swelling.
In the process, it is swollen by the way that polyvinyl alcohol resin film is made to impregnate 15 seconds~10 points in 20 DEG C~50 DEG C of solution
Clock is realized.The preferred water of solution at this time, or glycerine, ethyl alcohol, ethylene glycol, propylene glycol, low molecular poly etc.
The mixed solution of water-miscible organic solvent or water and water-miscible organic solvent.In process is swollen, fold or folding line in order to prevent
Generation, it is also preferred that appropriateness is stretched, stretching ratio is preferably 1.00~1.50 times, more preferably 1.10~1.35 times.
In the case where shortening the time for making polarizer, due to can also be obtained in iodine, iodide processing, in the dyeing process of dyestuff
To swelling effect, thus the process can also be omitted.
(dyeing process)
It is carried out next, being supplied to the above-mentioned polyvinyl alcohol resin film after swelling using the solution containing dichroism pigment
The dyeing process of dyeing.
As the solvent of solution, preferably water, but it is not particularly limited.As dichroism pigment, for example, by iodine
The more iodide ions obtained with the mixed solution of iodide or the dichroic dye of organic compound etc..As iodide, such as can
To use potassium iodide, ammonium iodide, cobaltous iodide, zinc iodide etc., but it is not limited to iodide shown herein.Iodine and iodide it is mixed
Close the iodine concentration in solution for the weight % of 0.0001 weight %~0.5, be preferably the weight % of 0.001 weight %~0.4.It is used
The concentration of iodide be preferably the weight % of 0.0001 weight %~8.According to circumstances, for correction of color, as organic compound
The dichroic dye of object, such as dichroism pigment etc. described in non-patent literature 1 can be used to want not damaging the application
Color correction is carried out in the range of the performance asked.Dyestuff does not limit, and can use well known dichroic dye.Dye strength does not have
It is particularly limited to, such as can be weight % of 0.006 weight %~0.3 or so.In the case that dyeability is insufficient, preferably add
The colouring aids such as sodium tripolyphosphate and/or saltcake (sodium sulphate) are dyed.In addition, dyeing temperature is 5 DEG C~50 DEG C, preferably
For 5 DEG C~40 DEG C, more preferably 10 DEG C~30 DEG C.Dyeing time can be appropriate according to transmissivity of obtained polarizer etc.
It adjusts, is 30 seconds~6 minutes or so, more preferably 1 minute~5 minutes.In this process, the hair of fold and folding line in order to prevent
It is raw, it is also preferred that appropriateness is stretched.Its stretching ratio is preferably 0.90~2.00 times, more preferably 1.00~1.30 times.
In above-mentioned dyeing process, crosslinking agent and/or water-fast can be added into the solution containing above-mentioned dichroism pigment
Agent.As crosslinking agent, for example, can use the polyaldehydes such as boron compounds, glyoxal, the glutaraldehyde such as boric acid, borax, ammonium borate,
Titanium sub-group compounds such as the multicomponent isocyanate based compound of biuret form, isocyanurate type, end-sealed type etc., titanyl sulfate etc.,
It can also use glycol glycidyl ethers, polyamideepichlorohydrin etc. in addition.As resistance to hydrated agent, can enumerate
Oxydisuccinic acid, ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether,
Ammonium chloride, magnesium chloride etc., preferred boric acid.On the concentration of addition, such as in the case where adding boric acid, compared with containing two colors
Property pigment solution be the weight % of 0.1 weight %~5.0, be preferably 2 weight %~4 weight %.And then as needed, above-mentioned
After dyeing process, before subsequent stretching process is entered, the polyvinyl alcohol resin film containing dichroism pigment can be carried out
Cleaning.As the solvent cleaned, generally using water, but can use alcohol series solvent, two alcohol series solvents, glycerine or they
Mixed solvent etc., is not particularly limited.In addition, temperature, time during cleaning according to the transmissivity of the polarizer as target,
The species of used dichroism pigment suitably adjusts.
(resistance to aquation treatment process)
Then, after dyeing process, for implementing the resistance to hydration process of resistance to hydration process to the film being colored as needed
Process.
In the process, above-mentioned film is handled using the solution containing crosslinking agent or/and resistance to hydrated agent.As crosslinking agent
Or/and resistance to hydrated agent, the polyaldehydes such as the boron compounds such as above-mentioned boric acid, borax, ammonium borate, glyoxal, glutaraldehyde, contracting can be enumerated
Titanium sub-group compounds, the second two such as the multicomponent isocyanate based compound of two urea types, isocyanurate type, end-sealed type etc., titanyl sulfate
Alcohol glycidol ether, polyamideepichlorohydrin, succinic acid peroxide, ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, second two
Alcohol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride, magnesium chloride etc., preferred boric acid.As the solvent at this point, such as
Water, alcohol series solvent, two alcohol series solvents, glycerine or their mixed solvent etc. can be used.On crosslinking agent or/and resistance to hydrated agent
Concentration, be preferably the dense of the weight % of 0.1 weight %~6.0 or so in the solution such as in the case of boric acid aqueous solution
Degree, more preferably the weight % of 2 weight %~4.Treatment temperature in the process is 5 DEG C~60 DEG C, is preferably 5 DEG C~45 DEG C left sides
It is right.Processing time is preferably 1 minute~5 minutes or so.In this process, the generation of fold and folding line in order to prevent, it is also preferred that
Appropriateness is stretched, and stretching ratio is 0.95~1.5 times or so.
(stretching process)
And then the stretching process for being stretched to polyvinyl alcohol resin film.
In the process, simple tension is carried out to the film.As drawing process, wet tensile method or dry type stretching can be used
Any one of method.
As the specific method of dry stretch process, for example, region pulling method, roller heating pulling method, pressurization between roller
Pulling method, infrared heating pulling method etc., are not particularly limited.Temperature during stretching is preferably room temperature~180 DEG C, and humidity is preferred
For 20%~95%RH or so.Stretching can be carried out with 1 stage, or the multistages more than 2 phase process stretches.
Wet tensile method is the method stretched in water, water-miscible organic solvent or its mixed aqueous solution, is preferably existed
Contain boron compounds, the second two such as above-mentioned boric acid, borax, ammonium borate in the water, water-miscible organic solvent or its mixed aqueous solution
Multicomponent isocyanate based compound, the sulfuric acid oxygen of the polyaldehydes such as aldehyde, glutaraldehyde, biuret form, isocyanurate type, end-sealed type etc.
The titanium sub-group compounds such as titanium, glycol glycidyl ethers, polyamideepichlorohydrin, succinic acid peroxide, ammonium persulfate, perchloric acid
The crosslinking agents such as the boric acid such as calcium, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether, ammonium chloride, magnesium chloride
Or/and stretch processing is carried out while dipping in the solution of resistance to hydrated agent, more preferably stretched in boric acid aqueous solution.Crosslinking
The concentration of agent or/and resistance to hydrated agent is preferably the weight % of the weight % of 0.5 weight %~8, more preferably 2.0 weight %~4.0.It draws
It is preferably 3~8 times, more preferably 5~7 times or so to stretch multiplying power.Draft temperature is preferably 40 DEG C~60 DEG C, more preferably 45 DEG C~
55℃.Stretching time is preferably 30 seconds~20 minutes, more preferably 2 minutes~5 minutes.Stretch processing can be 1 stage, also may be used
Think that 2 the multistage more than stage stretched.
Foreign matter or attachment is precipitated in the surface of the polyvinyl alcohol resin film containing dichroism pigment after the stretch sometimes
Foreign matter, thus can be cleaned.As the solvent cleaned, water, alcohol series solvent etc. can be used, but is not limited to this
A bit.It, can the crosslinking agent containing boric acid etc and/or resistance to hydrated agent in cleaning solvent in order to improve the durability of film.Crosslinking
The concentration of agent and/or resistance to hydrated agent does not limit, and is, for example, the weight % of 0.1 weight %~10.
(postprocessing working procedures)
Then, in order to adjust tone, improve polarization characteristic, raising durability, carry out after implementing post processing to above-mentioned film
Treatment process.
In the process, specifically, using the solution containing chloride or iodide to containing dichroism pigment and carrying out
The polyvinyl alcohol resin film of simple tension is handled.As chloride or iodide, for example, potassium iodide, iodine
Change chloride of sodium, ammonium iodide, cobaltous iodide, the iodide of zinc iodide etc, zinc chloride, potassium chloride, sodium chloride etc etc., it can be with
One or more therein are mixed into solution to handle.The concentration of chloride or iodide in solution is preferred
For the weight % of the weight % of 0.1 weight %~15, more preferably 0.15 weight %~10.In this process, in order to prevent fold and
The generation of folding line, it is also preferred that appropriateness is stretched, stretching ratio at this time is preferably 0.90~1.10 times.In addition, treatment temperature
Such as it is preferably 5 DEG C~less than 50 DEG C, more preferably 20 DEG C~40 DEG C.Processing time is, for example, 1 second~5 minutes or so, preferably
For 5 seconds~30 seconds.In the process, above-mentioned crosslinking agent and/or resistance to hydrated agent can be added.The concentration of addition is, for example, 0.5 weight
Measure the weight % of %~10.
As the solvent used in treatment process so far, for example, water, dimethyl sulfoxide (DMSO), N- crassitudes
Ketone, methanol, ethyl alcohol, propyl alcohol, isopropanol, glycerine, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or three hydroxyls
The amines equal solvent such as the alcohols such as methylpropane, ethylenediamine or diethylenetriamines, but it is not limited to these.Alternatively, it is also possible to make
With the mixture of a kind of the above solvent.Most preferred solvent is water.
(drying process)
By drying process after above-mentioned postprocessing working procedures, the base material of the polarizer of the present invention is thus obtained.
As dry method, for example, spontaneously drying；Compression, air knife or the suction roll carried out by using roller
Deng the method for removing surface moisture；By heating drying carried out etc..Drying temperature during as heat drying is preferably 20 DEG C
~90 DEG C, more preferably 40 DEG C~70 DEG C.Drying time is preferably 30 seconds~20 minutes or so, more preferably 2 minutes~10 points
Clock or so.In the drying process, the fold caused by the contraction of the polyvinyl alcohol resin film associated with drying in order to prevent
Or the generation of striped, it is also preferred that moderately being stretched, stretching ratio at this time is preferably 0.95~1.10 times.
By above-mentioned swelling process, dyeing process, optional resistance to aquation treatment process, stretching process, postprocessing working procedures and
Thus drying process obtains the base material of polarizer.Also, so obtained base material is by the hydrophilic of absorption boric acid and drawn
Property the base material with polarization function containing iodine that forms of macromolecule, contained in the form of free acid represented by following formula (1)
Organic compound or its salt, visibility correction single plate transmission Ys when being measured using its monolithic as 40.0%~
42.5%, the single plate transmission Ts of visibility correction single plate transmission Ys and 460nm460Difference within 1.2%, visibility school
The single plate transmission Ts of positive single plate transmission Ys and 550nm550Difference within 1%, visibility correction single plate transmission Ys with
The single plate transmission Ts of 610nm610Difference within 1%, make the absorption direction of principal axis of 2 base materials orthogonally to 2 base materials into
It is less than 0.01% that row, which measures obtained visibility correction of orthogonal transmissivity Yc, and the absorption direction of principal axis for making 2 base materials is orthogonal
The average value for the orthogonal transmission that ground is measured obtained 430nm~480nm to 2 base materials be adjusted to 0.03% with
Under.
[changing 2]
(in formula (1), R1Represent that hydrogen atom, halogen atom, low alkyl group, lower alkoxy or carboxyl, k, m, n represent 0 respectively
Or 1.Wherein, m+n>1.)
Possesses the polarizer of the base material with above-mentioned characteristic in order to obtain, it is necessary to the organic compound containing formula (1).And
And as the method that base material is made to contain the organic compound, dyeing process that base material contains dichroism pigment, optionally can be made
Resistance to aquation treatment process, stretching process, postprocessing working procedures any process in, to base in the solution containing organic compound
Material carries out infiltration processing and base material is made to contain the organic compound, preferably following methods：Make polyvinyl alcohol resin membrane swelling
Afterwards, before the process dyed in iodine and iodine compound, further setting process and method that base material is made to contain the organic compound；
The method that base material is made to contain the organic compound while dyeing process that base material is made to contain dichroism pigment；After iodine staining,
Setting process and method that base material is made to contain the organic compound before the stretching；Simultaneously base material is made to contain this in postprocessing working procedures
The method of organic compound.And then the work dyed more preferably after polyvinyl alcohol resin membrane swelling is made, in iodine and iodine compound
Setting process before sequence and the method contained.
As the concrete example of the pigment represented by formula (1), C.I. directly Huang 28, C.I. directly Huang 29 can be exemplified.Formula (1)
The concentration of organic compound be not particularly limited, for example, left for 0.05 parts by weight~3 parts by weight compared with 1000 parts by weight of water
The right side is suitable, in the case where dyeability is insufficient, preferably adds the colorings such as sodium tripolyphosphate and/or saltcake (sodium sulphate) and helps
Agent is dyed.In addition, dyeing temperature is 5 DEG C~50 DEG C, is preferably 5 DEG C~40 DEG C, more preferably 10 DEG C~30 DEG C.Dyeing
Time can suitably be adjusted according to transmissivity of obtained polarizer etc., such as can be 30 seconds~6 minutes or so, preferably
For 1 minute~5 minutes.
Then, the more specific example of the pigment represented by formula (1) is shown in the form of free acid as follows.
[compound example 1]
[changing 2]
[compound example 2]
[changing 3]
[compound example 3]
[changing 4]
In addition, in postprocessing working procedures, using containing the chloride with debita spissitudo or the solution of iodide to containing
Dichroism pigment and carried out simple tension polyvinyl alcohol resin film carry out processing be critically important.In the process, it is necessary to
The concentration of the chloride contained in solution or iodide and its processing time are adjusted according to stretching condition.When the concentration and processing
Between according to infiltration situation of the chlorides such as the iodide such as iodine and potassium iodide and potassium chloride in polarizer be to be adjusted
It is very important.Particularly, concentration is also stretched the tensional state of process, the temperature and humidity in the place for making polarizer
Deng influence, thus need very careful micro-adjustment.In general, on the chloride used in postprocessing working procedures solution or
The concentration of solution containing iodide, compared with 1000 parts by weight of water, the weight of 1.0 parts by weight of addition chloride or iodide~150
Part, preferably add the parts by weight of 1.5 parts by weight~100 to be prepared.
Additionally, it is preferred that keep stretch after stretching ratio and/or tensile stress with do not occur as far as possible the contraction of film or
It is handled while expansion.Furthermore it is preferred that in the transfer rate of film and the water velocity of postprocessing working procedures, there is no relatively fast
It is handled in the state of degree difference, in addition, more preferably fully being handled at this time to polarizer using ultrasonic wave treatment fluid
Portion.Postprocessing working procedures are carried out by the above method, the polarizer of the application can be obtained.
Index for having the manufacture adjustment of more good performance as polarizer is under the 255nm of ultraviolet region
Transmissivity.It is absorbed this is because the organic compound shown in formula (1) has in 255nm, thus contains the compound in the substrate
In the case of, it may determine whether by the 255nm of ultraviolet region as the polarizer with superperformance.Iodine or iodine compound
Ultraviolet region absorption be 220nm, 295nm and 360nm absorption, it is different from the absorption of the organic compound of formula (1), thus
Can the suitably compound of adjustment type (1) content.In order to assign good polarization characteristic, compound on formula (1)
Content, it is preferred that the visibility correction when absorption direction of principal axis of 2 plate substrates being made parallelly to be measured to 2 plate substrates is parallel
Transmissivity Yp is 33%~37% scope, and parallel transmission Yp is with making the absorption direction of principal axis of 2 base materials parallelly to 2
The transmissivity Tp of 255nm when the base material is measured255Meet following formula (2).More preferably meet formula (2B).
0.75×Yp-13≤Tp255≤ 0.75 × Yp+1.0 formulas (2)
0.75×Yp-11≤Tp255≤ 0.75 × Yp formulas (2B)
In addition, in order to have more good polarization characteristic, the index of the content of the compound as definite formula (1), preferably
, when the absorption direction of principal axis of 2 plate substrates being made parallelly to be measured to 2 plate substrates visibility correction parallel transmission Yp be
33%~37% scope, parallel transmission Yp is with making the absorption direction of principal axis of 2 base materials orthogonally be carried out to 2 base materials
The transmissivity Tc of 255nm during measure255Meet following formula (3).
2.0×10-6×Yp4.1≤Tc255≤2.0×10-6×Yp4.4Formula (3)
In addition, not only need the content of the organic compound shown in adjustment type (1), it is also necessary to adjust iodine and iodine compound
Content.In particular, it may be desired to the visibility correction when absorption direction of principal axis of 2 plate substrates being made parallelly to be measured to 2 plate substrates
Parallel transmission Yp is 33%~37% scope, and parallel transmission Yp is with making the absorption direction of principal axis of 2 plate substrates parallelly to 2
The transmissivity Tp of 460nm when plate substrate is measured460Difference be adjusted within 3%.In order to make Yp and Tp460Difference be 3%
Within, it is necessary to adjust the transmissivity of the 295nm when absorption direction of principal axis of 2 plate substrates being made parallelly to be measured to 2 plate substrates
Tp295With the transmissivity Tp of 360nm360.It is said that the transmissivity Tp of the 295nm295And the transmissivity Tp of the 360nm360Because of polarization
I in element3 -、I5 -It is changed etc. the content of more iodine.By adjusting the I in polarizer3 -、I5 -Etc. the content of more iodine, can adjust
The transmissivity of whole 295nm and 360nm, can be by Yp and Yp460Difference be adjusted within 3%.
In order to manufacture better polarizer, it is necessary to be adjusted to：Make the absorption direction of principal axis of 2 base materials parallelly to 2
The base material is measured the scope that obtained visibility correction transmissivity Yp is 33%~37%, and transmissivity Yp is with making 2
The transmissivity Tp of 295nm when the absorption direction of principal axis of the base material is parallelly measured 2 base materials295Meet following formula
(4), and the above-mentioned Yp and 360nm when absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials it is saturating
Penetrate rate Tp360Meet following formula (5).
1.05×Yp-26≤Tp295≤ 1.05 × Yp-13 formulas (4)
1.25×Yp-26.25≤Tp360≤ 1.25 × Yp-16.25 formulas (5)
In order to further improve the performance of polarizer, polarizer is particularly improved in the 380nm as visibility region
The performance of~480nm is, it is necessary to improve the I of 295nm, 360nm3 -、I5 -Etc. the orientation of more iodine, more preferably meet above-mentioned formula (4) and
Formula (5), and then the transmissivity of the 295nm when absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials
Tc295Meet following formula (6), the 360nm's when absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials
Transmissivity Tc360Meet following formula (7).It should be noted that in following formula, Yp18.6、Yp19.4、Yp22.12And Yp22.67Respective table
Show the multiplier of parallel transmission Yp.
2.0×10-30×Yp18.6≤Tc295≤2.0×10-30×Yp19.4Formula (6)
4.0×10-37×Yp22.12≤Tc360≤4.0×10-37×Yp22.67Formula (7)
In addition, in LED backlight in recent years, using fluorophor the blue light of 460nm is made to send white light, thus with
The transmissivity of 430nm~480nm centered on 460nm is critically important to the contrast for improving polarizer.Particularly, in 460nm
Under polarizer when the absorption direction of principal axis of 2 plate substrates being made orthogonally to be measured to 2 plate substrates transmissivity it is high when, blue light
It can leak out, pure black can not be shown as display.If in addition, at this point, the transmissivity of 610nm compared with 460nm not
With constant transmissivity following to a certain degree, then pure black can not be equally shown, can not realize white and black
Comparison.Accordingly, with respect to the transmissivity of polarizer, it is preferably regulated as：Make the absorption direction of principal axis of 2 plate substrates orthogonally to 2
The transmissivity of 460nm when base material is measured is less than 0.035%, and makes the absorption direction of principal axis of 2 plate substrates orthogonally to 2
The transmissivity of 610nm when plate substrate is measured is less than 0.01%.
And then for this purpose, by using the polyethenol series for being 1000~10000 by the degree of polymerization of polyvinyl alcohol resin film
Base material of the base film that resin film is formed as polarizer, can easily realize the application.More preferable polyvinyl alcohol mesentery
The degree of polymerization is 3500~6000, and the further preferred degree of polymerization is 4500~6000.
<Polarizer>
It is set by at least single or double of the polarizer of the present invention obtained in process more than process transparency protected
Layer can obtain the polarizer of the present invention.Specifically, transparent protective layer can by will be formed the protective layer polymer or
Film is coated with or lamination is set on the polarizer of the present invention.It is excellent as the transparent polymer or film for forming transparent protective layer
Select high mechanical strength, the transparent polymer or film of good thermal stability.And then the excellent polymer of more preferable moisture barrier or
Film.As the substance as transparent protective layer, for example, the second of triacetyl cellulose or diacetyl cellulose etc
Acid cellulose resin or its film, acrylic resin or its film, polyester resin or its film, polyarylate resin or its film, to drop ice
The cyclic olefin of piece alkene etc is the cyclic polyolefin resin of monomer or its film, polyethylene, polypropylene, poly terephthalic acid second two
Alcohol ester, ring system have the tree of polyolefin or its copolymer of norbornene skeleton, main chain or side chain for acid imide and/or amide
Fat or polymer or its film etc..Furthermore it is known that polyvinyl alcohol resin is functioned usually as alignment films, thus can be to institute
The surface applications of obtained polarizer are set such as friction treatment or alignment films coating and orientation process with liquid crystal liquid crystal property
Resin or its film.The thickness of protective film is, for example, 0.5 μm~200 μm or so.In two-sided these films of setting of polarizer
In the case of, identical film can be used, different films can also be used.
In the case of the film and the polarizer lamination of the present invention that will be used as above-mentioned transparent protective layer, it is preferable to use bondings
Agent.As bonding agent, for example, polyethenol series, carbamate system, acrylic acid series, epoxy bonding agent.As
Polyethenol series bonding agent, for example, Gohsenol NH-26 (manufacture of synthesis society of Japan), Exceval RS-2117
(manufacture of KURARAY societies) etc., but it is not limited to these.Crosslinking agent and/or resistance to hydrated agent can be added in bonding agent.In addition,
Can inorganic acid or its salt and/or organic acid be contained with the concentration of the weight % of 0.0001 weight %~20 in bonding agent, preferably
Containing 0.02 weight %~5 weight %.It can be used alone maleic anhydride-isobutylene copolymers in polyethenol series bonding agent
Object can use the bonding agent mixed together with crosslinking agent.As maleic anhydride-isobutylene copolymers, such as can
Isobam#104 is modified to enumerate Isobam#18 (manufacture of KURARAY societies), Isobam#04 (manufacture of KURARAY societies), ammonia
(manufacture of KURARAY societies), ammonia are modified Isobam#110 (manufacture of KURARAY societies), imidizate Isobam#304 (KURARAY societies
Manufacture), imidizate Isobam#310 (manufacture of KURARAY societies) etc..Water-soluble polynary ring can be used in crosslinking agent at this time
Oxygen compound.Water-soluble polynary epoxide is for example, Denacol EX-521 (Nagase ChemteX societies systems
Make), Tetrad-C (manufacture of gas chemistry society of Mitsubishi) etc..In addition, the additive as bonding agent, by containing above-mentioned buffering
Agent, inorganic acid or its salt and/or organic acid, zinc compound, chloride or iodide etc., more preferably compared with bonding agent ingredient with
The concentration of the weight % of 0.01 weight %~10 or so contains above-mentioned buffer, inorganic acid or its salt and/or organic acid, equally can be with
Improve durability.After by the use of above-mentioned bonding agent using being bonded as the film of transparent protective layer with the polarizer of the present invention, carry out
Heat drying, and then be heat-treated, it is possible thereby to be bonded.
It is filtered in the case where obtained polarizer to be fitted in the display device such as liquid crystal display or in polarization
In light device or polarized lens in the case of use, it can also set and use on the surface for the protective layer or film for becoming non-exposed surface afterwards
In the layer or film that improve the various functions layer at visual angle and/or improvement contrast, there is brightness raising property.In order to which polarizer is pasted
It is bonded in these films or display device, it is preferable to use adhesives.
The polarizer can have anti-reflecting layer, antiglare layer, hard in the exposed surface of another surface, i.e. protective layer or film
Various functions layer well known to coating etc..In order to make the layer with various functions, preferably it is arranged at by coating method
Another surface, but the functional film of the tool can also be bonded by bonding agent or adhesive.In addition, various functions layer can
To set the layer or film of phase difference in order to control.
By method described above, can obtain high with constant transmissivity and contrast under each wavelength
Polarizer or polarizer.The polarizer or polarizer of the so obtained present invention with high polarization property, i.e. high comparison
While spending, each Thewavelengthtransmittance that can make visibility region is constant, and excellent in te pins of durability, thus can remain stable for a long time
Performance.
<Liquid crystal display device>
And then by the way that the polarizer of the present invention in liquid crystal display, el display device, CRT etc., can be obtained
To the image display device of the present invention.Particularly, by the way that the polarizer of the present invention is utilized bonding with phase difference film as needed
Agent conforms to the both sides for the liquid crystal cells for forming liquid crystal display together, can obtain liquid crystal display device.
Embodiment
Below by embodiment, the present invention will be described in more detail, but the present invention is not limited to this.
The evaluation of the transmissivity shown in each embodiment carries out as follows.
The transmissivity of each wavelength when measuring 1 polarizer or polarizer is set to single plate transmission Ts, by 2 polarizations
The transmissivity of each wavelength when element or polarizer are overlapped in a manner that its absorption direction of principal axis is identical is set to parallel transmission Tp, will
The transmissivity of each wavelength when 2 polarizers are overlapped in a manner that its absorption axis is orthogonal is set to orthogonal position transmissivity Tc.
Spectral transmission Ts, Tp and Tc are each measured using spectrophotometer [" U-4100 " that society of Hitachi manufactures].
Visibility correction single plate transmission Ys is calculated as follows：In the wavelength region of 400nm~700nm, every defined
Wavelength interval d λ (being herein 5nm) measure single plate transmission Ts, are calculated by single plate transmission Ts according to following formula (8).In formula, P λ
The light splitting distribution of expression standard light (illuminant-C), y λ represent the color matching functions based on JIS Z 8729 (2 ° of visuals field of illuminant-C).
Visibility correction parallel transmission Yp is calculated as follows：In the wavelength region of 400nm~700nm, every defined
Wavelength interval d λ (being herein 5nm) measure parallel transmission Tp, are calculated by parallel transmission Tp according to following formula (9).In formula, P λ
The light splitting distribution of expression standard light (illuminant-C), y λ represent the color matching functions based on JIS Z 8729 (2 ° of visuals field of illuminant-C).
Visibility correction of orthogonal transmissivity Yc is calculated as follows：In the wavelength region of 400nm~700nm, every defined
Wavelength interval d λ (being herein 5nm) measure orthogonal transmission Tc, are calculated by orthogonal transmission Tc according to following formula (10).In formula, P
λ represents the light splitting distribution of standard light (illuminant-C), and y λ represent the color matching functions based on JIS Z 8729 (2 ° of visuals field of illuminant-C).
Degree of polarization Py corrects parallel position transmissivity Yp and visibility correction of orthogonal transmissivity Yc according to following formula by visibility
(11) it is obtained.
Py=100x { (Yp-Yc)/(Yp+Yc) }1/2Formula (11)
Embodiment 1
Make the polyethenol series that thickness is 60 μm, the degree of polymerization 5500, saponification degree are more than 99% using 40 DEG C of warm water
After the film VF-PM of manufacture (KURARAY societies) swelling, using contain 1000 parts by weight of water, international publication number WO2005/015275 is closed
The aqueous solution processing 1 of 0.02 parts by weight of pigment, 1.0 parts by weight of sodium tripolyphosphate into the structure with formula (1) described in example 1
Points 30 seconds, followed by containing 1000 parts by weight of water, boric acid (manufacture of Societa larderello s.p.a. societies) 28.6 weight
Part, iodine (manufacture of pure chemistry society) 0.14 parts by weight, the aqueous solution of potassium iodide (manufacture of pure chemistry society) 10.27 parts by weight are 30
DEG C dipping 2 minutes, carry out dyeing processing.Film after dyeing is stretched 5 times in the solution containing 3 weight % boric acid in 58 DEG C,
After stretching, in the aqueous solution containing iodide for adding 3.5 parts by weight of potassium iodide compared with 1000 parts by weight of water and making, protecting
Stretching ratio is maintained while holding the tension after stretching, in the transfer rate and the water velocity for the treatment of process handled film
Relative velocity difference constant in the state of, using 20kHz~40kHz ultrasonic wave and meanwhile dipping, carry out 20 seconds
Postprocessing working procedures.It dries 10 minutes, is polarized impregnated of the drying machine using 70 DEG C after the film of 20 seconds potassium iodide aqueous solutions
Element.
Embodiment 2
Use polyvinyl alcohol mesentery (the KURARAY societies that thickness is 40 μm, the degree of polymerization 4000, saponification degree are more than 99%
The VF-PH of manufacture) replace the polyvinyl alcohol mesentery that thickness is 60 μm, the degree of polymerization 4000, saponification degree are more than 99%
(VF-PM of KURARAY societies manufacture) obtains the polarizer of the application similarly to Example 1 in addition.
Embodiment 3
Except the time that dyeing is handled is made in addition to 30 seconds, to obtain polarizer similarly to Example 2 for 1 point.
Embodiment 4
Except the time that dyeing is handled is made in addition to 30 seconds, to obtain polarizer similarly to Example 1 for 1 point.
Embodiment 5
Make the polyethenol series that thickness is 60 μm, the degree of polymerization 5500, saponification degree are more than 99% using 40 DEG C of warm water
After the film VF-PM of manufacture (KURARAY societies) swelling, using contain 1000 parts by weight of water, international publication number WO2005/015275 is closed
The aqueous solution processing 1 of 0.02 parts by weight of pigment, 1.0 parts by weight of sodium tripolyphosphate into the structure with formula (1) described in example 1
Divide 30 seconds, then containing 1000 parts by weight of water, boric acid (manufacture of Societa larderello s.p.a. societies) 28.6 weight
Part, in the aqueous solution of iodine (pure chemistry society manufacture) 0.14 parts by weight, potassium iodide (manufacture of pure chemistry society) 10.27 parts by weight in
30 DEG C impregnate 2 minutes, carry out dyeing processing.Film after dyeing is stretched 5 in the solution containing 3 weight % boric acid in 58 DEG C
Times, after stretching, stretching ratio is maintained while the tension after keeping stretching, in the transfer rate and processing handled film
It is impregnated in the state of the difference constant of the relative velocity of the water velocity of process, carries out the postprocessing working procedures of 20 seconds.It
Afterwards, dried 10 minutes using 70 DEG C of drying machine, obtain polarizer.
Comparative example 1
Do not utilize containing described in 1000 parts by weight of water, international publication number WO2005/015275 synthesis examples 1 have formula
(1) aqueous solution of the pigment of structure is handled, followed by containing 1000 parts by weight of water, boric acid (Societa
Larderello s.p.a. societies manufacture) 28.6 parts by weight, iodine (pure chemistry society manufacture) 0.14 parts by weight, potassium iodide (pureization
Learn society's manufacture) aqueous solutions of 10.27 parts by weight impregnates 2 minutes in 30 DEG C, dyeing processing is carried out, also, after the stretch, compared with
1000 parts by weight of water add 35 parts by weight of potassium iodide, and made aqueous solution is stirred with the speed of 60rpm, while is being tieed up
It holds and carries out the postprocessing working procedures of 20 seconds in the state of the multiplying power after stretching, it is first to obtain polarization similarly to Example 1 in addition
Part.
Comparative example 2
Do not utilize containing described in 1000 parts by weight of water, international publication number WO2005/015275 synthesis examples 1 have formula
(1) aqueous solution of the pigment of structure is handled, followed by containing 1000 parts by weight of water, boric acid (Societa
Larderello s.p.a. societies manufacture) 28.6 parts by weight, iodine (pure chemistry society manufacture) 0.14 parts by weight, potassium iodide (pureization
Learn society's manufacture) aqueous solutions of 10.27 parts by weight impregnates 2 minutes in 30 DEG C, dyeing processing is carried out, also, after the stretch, compared with
1000 parts by weight of water add 35 parts by weight of potassium iodide, and made aqueous solution is stirred with the speed of 60rpm, while is being tieed up
It holds and carries out the postprocessing working procedures of 20 seconds in the state of the multiplying power after stretching, it is first to obtain polarization similarly to Example 2 in addition
Part.
Comparative example 3
Do not utilize containing described in 1000 parts by weight of water, international publication number WO2005/015275 synthesis examples 1 have formula
(1) aqueous solution of the pigment of structure is handled, followed by containing 1000 parts by weight of water, boric acid (Societa
Larderello s.p.a. societies manufacture) 28.6 parts by weight, iodine (pure chemistry society manufacture) 0.14 parts by weight, potassium iodide (pureization
Learn society's manufacture) aqueous solutions of 10.27 parts by weight impregnates 2 minutes in 30 DEG C, dyeing processing is carried out, also, after the stretch, compared with
1000 parts by weight of water add 50 parts by weight of potassium iodide, and made aqueous solution is stirred with the speed of 60rpm, while is being tieed up
It holds and carries out the postprocessing working procedures of 20 seconds in the state of the multiplying power after stretching, it is first to obtain polarization similarly to Example 3 in addition
Part.
Comparative example 4
Do not utilize containing described in 1000 parts by weight of water, international publication number WO2005/015275 synthesis examples 1 have formula
(1) aqueous solution of the pigment of structure is handled, followed by containing 1000 parts by weight of water, boric acid (Societa
Larderello s.p.a. societies manufacture) 28.6 parts by weight, iodine (pure chemistry society manufacture) 0.14 parts by weight, potassium iodide (pureization
Learn society's manufacture) aqueous solutions of 10.27 parts by weight impregnates 2 minutes in 30 DEG C, dyeing processing is carried out, also, after the stretch, compared with
1000 parts by weight of water add 50 parts by weight of potassium iodide, and made aqueous solution is stirred with the speed of 60rpm, while is being tieed up
It holds and carries out the postprocessing working procedures of 20 seconds in the state of the multiplying power after stretching, it is first to obtain polarization similarly to Example 4 in addition
Part.
Comparative example 5
The iodine system polarizer SKN-18242P that Polatechno societies manufacture is impregnated into dichloromethane, extraction polarization member
Part, as comparative sample.
Comparative example 6
Do not utilize containing described in 1000 parts by weight of water, international publication number WO2005/015275 synthesis examples 1 have formula
(1) aqueous solution of the pigment of structure is handled, followed by containing 1000 parts by weight of water, boric acid (Societa
Larderello s.p.a. societies manufacture) 28.6 parts by weight, iodine (pure chemistry society manufacture) 0.25 parts by weight, potassium iodide (pureization
Learn society manufacture) 17.7 parts by weight aqueous solution in 30 DEG C impregnate 2 minutes, carry out dyeing processing, also, after the stretch, film soaked
Stain into water handle within 20 seconds, obtains polarizer similarly to Example 5 in addition.
Comparative example 7
Using containing described in 1000 parts by weight of water, international publication number WO2005/015275 synthesis examples 1 have formula (1)
0.1 parts by weight of pigment of structure, the aqueous solution of 1.0 parts by weight of sodium tripolyphosphate handle 3 points 00 second, in addition with embodiment
1 similarly makes polarizer.Obtained polarizer, which seems, is colored as yellow.
Each parameter of the polarizer obtained in Examples 1 to 5 and comparative example 1~7 is shown in table 1.Ginseng shown in table 1
Number is as described below.
Visibility corrects single plate transmission Ys,
Visibility corrects parallel transmission Yp,
Visibility correction of orthogonal transmissivity Yc,
The single plate transmission Ts of 460nm460,
The parallel transmission of 460nm when the absorption direction of principal axis of 2 plate substrates being made parallelly to be measured to 2 plate substrates
Tp460,
The orthogonal transmission of 460nm when the absorption direction of principal axis of 2 plate substrates being made orthogonally to be measured to 2 plate substrates
Tc460,
The single plate transmission Ts of 550nm550,
The single plate transmission Ts of 610nm610,
The orthogonal transmission of 610nm when the absorption direction of principal axis of 2 plate substrates being made orthogonally to be measured to 2 plate substrates
Tc610,
The average value Ts Ave430-480 of the single plate transmission of 430nm~480nm,
The parallel position of 430nm~480nm when the absorption direction of principal axis of 2 plate substrates being made parallelly to be measured to 2 plate substrates
Transmissivity average value Tp Ave430-480,
The orthogonal position of 430nm~480nm when the absorption direction of principal axis of 2 plate substrates being made orthogonally to be measured to 2 plate substrates
Transmissivity average value Tc Ave430-480.
【Table 1】
The further parameter obtained for Examples 1 to 5 and comparative example 1~7 is shown in table 2.Parameter shown in table 2
As described below.
Make the absorption direction of principal axis of 2 plate substrates that parallelly 2 plate substrates are measured with the parallel transmission of obtained 255nm
Tp255,
Make the absorption direction of principal axis of 2 plate substrates that orthogonally 2 plate substrates are measured with the orthogonal transmission of obtained 255nm
Tc255,
Make the absorption direction of principal axis of 2 plate substrates that parallelly 2 plate substrates are measured with the parallel transmission of obtained 295nm
Tp295,
Make the absorption direction of principal axis of 2 plate substrates that orthogonally 2 plate substrates are measured with the orthogonal transmission of obtained 295nm
Tc295,
Make the absorption direction of principal axis of 2 plate substrates that parallelly 2 plate substrates are measured with the parallel transmission of obtained 360nm
Tp360,
Make the absorption direction of principal axis of 2 plate substrates that orthogonally 2 plate substrates are measured with the orthogonal transmission of obtained 360nm
Tc360。
【Table 2】
| Tp255 | Tc255 | Tp295 | Tc295 | Tp360 | Tc360 | |
| Embodiment 1 | 21.409 | 9.822 | 12.664 | 0.255 | 19.509 | 0.019 |
| Embodiment 2 | 21.638 | 8.928 | 12.212 | 0.168 | 18.658 | 0.009 |
| Embodiment 3 | 23.074 | 10.442 | 13.854 | 0.270 | 19.876 | 0.020 |
| Embodiment 4 | 17.849 | 7.691 | 12.405 | 0.205 | 19.011 | 0.010 |
| Embodiment 5 | 20.479 | 7.527 | 21.798 | 0.766 | 25.663 | 0.008 |
| Comparative example 1 | 31.730 | 13.424 | 8.090 | 0.020 | 14.319 | 0.013 |
| Comparative example 2 | 35.080 | 20.037 | 9.716 | 0.066 | 16.663 | 0.059 |
| Comparative example 3 | 33.431 | 17.686 | 9.691 | 0.042 | 17.000 | 0.042 |
| Comparative example 4 | 35.157 | 23.099 | 12.315 | 0.190 | 19.210 | 0.191 |
| Comparative example 5 | 37.715 | 27.996 | 8.044 | 0.192 | 14.796 | 0.318 |
| Comparative example 6 | 33.094 | 15.732 | 24.765 | 1.836 | 27.984 | 0.016 |
| Comparative example 7 | 11.080 | 4.322 | 12.565 | 0.215 | 19.210 | 0.020 |
It can be seen from the above result that the polarizer of Examples 1 to 5 is the transmissivity for having under each wavelength constant
Polarizer, visibility when being measured using monolithic correct single plate transmission Ys as 40.0%~42.5%, visibility correction monolithic
The single plate transmission Ts of transmissivity Ys and 460nm460Difference within 1.2%, visibility correction single plate transmission Ys and 550nm
Single plate transmission Ts550Difference within 1%, the single plate transmission Ts of visibility correction single plate transmission Ys and 610nm610It
Difference is within 1%, and the absorption direction of principal axis of 2 base materials is made orthogonally to be measured obtained visibility school to 2 base materials
Positive orthogonal transmission Yc is less than 0.01%, and making the absorption direction of principal axis of 2 base materials, orthogonally to 2, the base material is measured institute
The average value Tc Ave430-480 of the orthogonal transmission of obtained 430nm~480nm are less than 0.03%.
In addition, carrying out lamination to polarizer by using protective layer, polarizer, the polarization of Examples 1 to 5 can be obtained
When absorption axiss are set in parallel, the transmissivity of 430nm~480nm has element compared with the transmissivity of 500nmm~650nm
There is the optical characteristics of constant, the uniformity of luminance under each wavelength can be kept.In addition, visibility correction of orthogonal transmissivity Yc
For less than 0.01%, and the average value Tc Ave430-480 of the orthogonal transmission of 430nm~480nm are less than 0.03%, thus
Will also realize that these polarizers is the polarizer for having high contrast and each Thewavelengthtransmittance of visibility region being made constant
Or polarizer.
Therefore, the polarizer of the Examples 1 to 5 obtained using the above method is made inclined using these polarizers
The piece that shakes can be used as transmissivity height, particularly contrast display polarizer more very high than high and color reprodubility, liquid
Crystal display is used with polarizer.In addition, use the display of the polarizer or polarizer that can expect to become reliable
Property it is high, high contrast and the display with high color reprodubility can be maintained for a long time.
Claims (11)
1. a kind of polarizer, formed it includes the hydrophilic macromolecule by absorption boric acid and drawn and the tool containing iodine
There is the base material of polarization function, which is characterized in that,
Contain the organic compound or its salt represented by formula (1) in the form of free acid,
[changing 1]
In formula (1), R1Represent that hydrogen atom, halogen atom, low alkyl group, lower alkoxy or carboxyl, k, m, n represent 0 or 1 respectively,
In, m+n>1,
The visibility when base material is measured using monolithic corrects single plate transmission Ys as 40.0%~42.5%,
The single plate transmission Ts of visibility correction single plate transmission Ys and 460nm460Difference within 1.2%,
The single plate transmission Ts of visibility correction single plate transmission Ys and 550nm550Difference within 1%,
The single plate transmission Ts of visibility correction single plate transmission Ys and 610nm610Difference within 1%,
Visibility correction of orthogonal transmissivity when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials
For less than 0.01%,
430nm~480nm's when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials is orthogonal
The average value Tc Ave430-480 for penetrating rate are less than 0.03%.
2. polarizer as described in claim 1, which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials is parallel
The scope that rate Yp is 33%~37% is penetrated,
The parallel transmission Yp of the base material and when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials
255nm transmissivity Tp255Meet following formula (2)：
0.75×Yp-13≤Tp255≤ 0.75 × Yp+1.0 formulas (2).
3. polarizer as claimed in claim 1 or 2, which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials is parallel
The scope that rate Yp is 33%~37% is penetrated,
The parallel transmission Yp and 255nm when absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials
Transmissivity Tc255Meet following formula (3)：
2.0×10-6×Yp4.1≤Tc255≤2.0×10-6×Yp4.4Formula (3).
4. polarizer as claimed in claim 1 or 2, which is characterized in that
Visibility correction when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials is parallel
The scope that rate Yp is 33%~37% is penetrated,
Parallel transmission Yp and when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials
The parallel transmission Tp of 460nm460Difference within 3%.
5. polarizer as claimed in claim 1 or 2, which is characterized in that
Visibility correction transmissivity when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials
Yp is 33%~37% scope,
Parallel transmission Yp and when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials
The transmissivity Tp of 295nm295Meet following formula (4),
Parallel transmission Yp and when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials
The transmissivity Tp of 360nm360Meet following formula (5),
1.05×Yp-26≤Tp295≤ 1.05 × Yp-13 ... formulas (4)
1.25×Yp-26.25≤Tp360≤ 1.25 × Yp-16.25 ... formulas (5).
6. polarizer as claimed in claim 1 or 2, which is characterized in that
The transmissivity Tc of 295nm when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials295
Meet formula (6), also,
The transmissivity Tc of 360nm when the absorption direction of principal axis of 2 base materials being made parallelly to be measured to 2 base materials360Meet
Formula (7),
2.0×10-30×Yp18.6≤Tc295≤2.0×10-30×Yp19.4... formula (6)
4.0×10-37×Yp22.12≤Tc360≤4.0×10-37×Yp22.67... formula (7).
7. polarizer as claimed in claim 1 or 2, which is characterized in that
The transmissivity Tc of 460nm when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials460
For less than 0.035%, also,
The transmissivity Tc of 610nm when the absorption direction of principal axis of 2 base materials being made orthogonally to be measured to 2 base materials610For
Less than 0.01%.
8. polarizer as claimed in claim 1 or 2, which is characterized in that
The base material is made of polyvinyl alcohol resin film,
The degree of polymerization of the polyvinyl alcohol resin film is 3000~7000.
9. a kind of polarizer is at least single side setting supporter in polarizer according to any one of claims 1 to 8
What film formed.
10. a kind of liquid crystal display device possesses polarizer according to any one of claims 1 to 8 or claim 9 institute
The polarizer stated.
11. a kind of manufacturing method of polarizer, which includes the hydrophilic macromolecule by absorption boric acid and drawn
It forms and the base material with polarization function containing iodine, the manufacturing method is characterized in that,
Including following processes：
(i) process for obtaining the film containing dichroism pigment in polyvinyl alcohol resin film containing dichroism pigment is made；
(ii) process that the film containing dichroism pigment is stretched into the film for obtaining drawn；
(iii) process that the solution using chloride or the solution containing iodide post-process the film of the drawn；
With
(iv) make film dry after processing in the rear and obtain the process of the base material,
The concentration of the solution of the chloride or solution containing iodide is the weight % of 0.1 weight %~15,
The process that the manufacturing method further comprises making the organic compound containing following formula (1) in base material,
[changing 1]
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013249360 | 2013-12-02 | ||
| JP2013-249360 | 2013-12-02 | ||
| PCT/JP2014/081789 WO2015083673A1 (en) | 2013-12-02 | 2014-12-01 | High-contrast polarization element exhibiting uniform transmittance at respective wavelengths, and polarization plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105899979A CN105899979A (en) | 2016-08-24 |
| CN105899979B true CN105899979B (en) | 2018-06-05 |
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| CN201480063578.XA Active CN105899979B (en) | 2013-12-02 | 2014-12-01 | The polarizer and polarizer of the high contrast with uniform transmissivity under each wavelength |
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| Country | Link |
|---|---|
| JP (1) | JP6461007B2 (en) |
| KR (1) | KR20160092985A (en) |
| CN (1) | CN105899979B (en) |
| HK (1) | HK1222712A1 (en) |
| TW (1) | TWI635327B (en) |
| WO (1) | WO2015083673A1 (en) |
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| CN116082266A (en) * | 2021-11-03 | 2023-05-09 | 广州华睿光电材料有限公司 | Organic compounds, mixtures, compositions, light extraction layer materials and organic electronic devices |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09133809A (en) * | 1995-11-09 | 1997-05-20 | Nippon Synthetic Chem Ind Co Ltd:The | Polarizing plate |
| JP2004341503A (en) * | 2003-04-21 | 2004-12-02 | Nitto Denko Corp | Polarizer, method for producing the same, polarizing plate, optical film and image display |
| JP2005049698A (en) * | 2003-07-30 | 2005-02-24 | Fuji Photo Film Co Ltd | Polarizing plate |
| WO2005029143A1 (en) * | 2003-09-19 | 2005-03-31 | Nippon Kayaku Kabushiki Kaisha | Polarizing film, polarizing plate and liquid crystal display device |
| JP2006276236A (en) * | 2005-03-28 | 2006-10-12 | Nippon Kayaku Co Ltd | Polarizing element film or polarizing plate |
| JP2008134270A (en) * | 2006-10-27 | 2008-06-12 | Nitto Denko Corp | Liquid crystal panel and liquid crystal display apparatus |
| JP2010091811A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Chemical Co Ltd | High contrast polarizing plate and liquid crystal display apparatus |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002258043A (en) * | 2001-03-02 | 2002-09-11 | Nitto Denko Corp | Polarizing plate and liquid crystal display device using the same |
| US7651643B2 (en) * | 2003-04-21 | 2010-01-26 | Nitto Denko Corporation | Polarizer, method for producing same, polarizing plate, optical film, and image display |
| JPWO2005015275A1 (en) * | 2003-08-07 | 2007-09-27 | 日本化薬株式会社 | Dye-type polarizing plate |
| JP2005202367A (en) | 2003-12-18 | 2005-07-28 | Nitto Denko Corp | Polarizer, optical film, and image display device |
-
2014
- 2014-12-01 KR KR1020167007188A patent/KR20160092985A/en not_active Application Discontinuation
- 2014-12-01 TW TW103141719A patent/TWI635327B/en active
- 2014-12-01 JP JP2015551505A patent/JP6461007B2/en active Active
- 2014-12-01 CN CN201480063578.XA patent/CN105899979B/en active Active
- 2014-12-01 WO PCT/JP2014/081789 patent/WO2015083673A1/en active Application Filing
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- 2016-09-14 HK HK16110897.5A patent/HK1222712A1/en not_active IP Right Cessation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09133809A (en) * | 1995-11-09 | 1997-05-20 | Nippon Synthetic Chem Ind Co Ltd:The | Polarizing plate |
| JP2004341503A (en) * | 2003-04-21 | 2004-12-02 | Nitto Denko Corp | Polarizer, method for producing the same, polarizing plate, optical film and image display |
| JP2005049698A (en) * | 2003-07-30 | 2005-02-24 | Fuji Photo Film Co Ltd | Polarizing plate |
| WO2005029143A1 (en) * | 2003-09-19 | 2005-03-31 | Nippon Kayaku Kabushiki Kaisha | Polarizing film, polarizing plate and liquid crystal display device |
| JP2006276236A (en) * | 2005-03-28 | 2006-10-12 | Nippon Kayaku Co Ltd | Polarizing element film or polarizing plate |
| JP2008134270A (en) * | 2006-10-27 | 2008-06-12 | Nitto Denko Corp | Liquid crystal panel and liquid crystal display apparatus |
| JP2010091811A (en) * | 2008-10-08 | 2010-04-22 | Sumitomo Chemical Co Ltd | High contrast polarizing plate and liquid crystal display apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105899979A (en) | 2016-08-24 |
| WO2015083673A1 (en) | 2015-06-11 |
| HK1222712A1 (en) | 2017-07-07 |
| KR20160092985A (en) | 2016-08-05 |
| TW201529279A (en) | 2015-08-01 |
| JPWO2015083673A1 (en) | 2017-03-16 |
| TWI635327B (en) | 2018-09-11 |
| JP6461007B2 (en) | 2019-01-30 |
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