CN107430234A

CN107430234A - Polarizer and polarizer

Info

Publication number: CN107430234A
Application number: CN201680014838.3A
Authority: CN
Inventors: 望月典明
Original assignee: Nippon Kayaku Co Ltd; Polatechno Co Ltd
Current assignee: Nippon Kayaku Co Ltd; Polatechno Co Ltd
Priority date: 2015-03-26
Filing date: 2016-03-08
Publication date: 2017-12-01
Anticipated expiration: 2036-03-08
Also published as: CN107430234B; TW201700623A; JP6178539B2; JPWO2016152498A1; WO2016152498A1; HK1246402A1; TWI668275B; KR20170131340A

Abstract

With high-transmission rate and while high-contrast, the white of netrual colour can be shown when the absorption axiss of polarizer are abreast set, and the black of netrual colour can be shown when the absorption axiss of polarizer are normally located otherwise.By the mixture of iodine and the azo-compound with specific structure, the following tone for adjusting polarizer or polarizer：On a* values specified in JIS Z 8729 and b* values, a* values and b* values when single plate transmission determines are calculated as within 1 with absolute value, the two panels base material is calculated as relative to a* values and b* values obtained from direction of principal axis is abreast measured is absorbed with absolute value within 2, make the two panels base material be orthogonally measured relative to absorption direction of principal axis obtained from a* values and b* values be calculated as with absolute value within 2.

Description

Polarizer and polarizer

Technical field

The present invention relates to the polarizer and polarizer being made up of iodine and azo-compound.

Background technology

Polarizer is generally adsorbed onto on polyvinyl alcohol resin film simultaneously by the iodine or dichroic dye that make to be used as dichroism pigment It is orientated to manufacture.It is bonded what is be made up of triacetyl cellulose etc. by bond layer at least on one side in the polarizer Diaphragm and polarizer is made, for liquid crystal display device etc..Polarizer using iodine as dichroism pigment is referred to as iodine system Polarizer, on the other hand, the polarizer using dichroic dye as dichroism pigment is referred to as dyestuff system polarizer.Wherein, Dyestuff system polarizer possesses following feature：With high-fire resistance, high wet heat durability, high stability, and the band by coordinating The selectivity for the color come is high；On the other hand, compared to iodine system polarizer, with the iodine system polarizer phase with identical degree of polarization Than dyestuff system polarizer has the problem of transmissivity is low, i.e. contrast is low.Therefore, it is desirable to dyestuff system polarizer remains high durable Property, color preference is various, has high polarization characteristic with higher transmissivity.But even this color preference is various Dyestuff system polarizer, when polarizer so far shows white abreast being set relative to absorption axiss, be still Show the polarizer of yellow hue.If yellow hue when being be arranged in parallel to improve and making inhibits Huang when be arrangeding in parallel The polarizer of tone, then polarizer have be arranged at relative to absorption axiss be normal axis in the case of black be rendered as blueness The problem of.In order to realize the polarizer of netrual colour, it is necessary to be in the absence of the dependence of each wavelength in parallel position and orthogonal position Constant transmissivity, but also fail to obtain such polarizer so far.

As this parallel position is with orthogonal position color difference the reasons why, it is due to：Even if dichroism pigment is used to polarize member Part, identical wavelength dependency can not be also shown in parallel position and orthogonal position, i.e. dichroism is not constant, and each ripple Long transmissivity is not constant.

Herein, each wavelength dependency in iodine system polarizer is illustrated.Make by polyvinyl alcohol (hereinafter referred to as PVA) For base material and in the case of using iodine as dichroism pigment, generally there is the absorption centered on 480nm and 600nm.It is said that 480nm absorption is due to more iodine I₃ ^-With PVA complex compound, 600nm absorption is due to more iodine I₅ ^-With PVA complex compound.Close In the degree of polarization based on each wavelength, more iodine I₅ ^-It is higher than with the degree of polarization of PVA complex compound and is based on more iodine I₃ ^-With PVA complex compound Degree of polarization.Which results in following phenomenons：That is, if make transmissivity constant in the orthogonal position of each wavelength, the 600nm at parallel position Transmissivity be higher than 480nm, parallel position colour yellowly.If on the contrary, make transmissivity constant in parallel position, in orthogonal position When 600nm transmissivity be less than 480nm, therefore colour au bleu in orthogonal position.Visibility is based primarily upon further, since being not present High 550nm absorption, therefore, it is difficult to carry out color control.That is, because the degree of polarization (dichroic ratio) of each wavelength is non-constant, because This generates wavelength dependency.On this point, even if not being iodine system polarizer, for dichromatic azo-compound, Wavelength dependency is similarly different in parallel position and orthogonal position, is usually not shown in parallel position with orthogonal position mutually homochromy The pigment of tune.

So far, there is the difference of the species of dichromatic azo-compound according in general, there is also shown in parallel position Go out yellow, blue equiwavelength's dependence is shown in orthogonal position in the entirely different azo-compound of orthogonal position peace line position.Separately Outside, it is also different in the sensitivity for the light and shade that the offer of orthogonal position peace line position gives people by will also realize that with polarised light this point, thus Assuming that to carry out its color correction, it is also desirable to which color correction is carried out according to sensitivity.The transmissivity of each wavelength in parallel position and If not the transmissivity of each position constant of orthogonal position can not then be realized, specifically, it is necessary to be in not for constant value The state of the transmission rate dependence of each wavelength be present.Moreover in polarizer or polarizer, in parallel position and orthogonal position It must simultaneously meet the constant transmission rate dependence and then the degree of polarization with high-transmission rate and high-contrast, then each wavelength (dichroic ratio) must be constant.Even if simply in the case where a kind of azo-compound is applied into polarizer, wavelength dependency Also can be different in orthogonal position peace line position, moreover, in the case of mixture, if inexactly controlling every a kind of parallel position and just The transmissivity of friendship position and the relation and degree of polarization of dichroic ratio be not high, then can not realize the netrual colour polarizer of the application.Thus It can be seen that it is extremely difficult to obtain netrual colour polarizer, it is not that merely can be achieved with using the three primary colors of color.To It is constant by parallel position and the control of orthogonal position, the degree of polarization of each wavelength also must be identical, is extremely difficult.

Therefore, as polarizer, it is necessary to a kind of white that netrual colour is shown in white displays, be shown in black display Go out the polarizer of the black of netrual colour, but it is more than 35%, in white displays to be also difficult to obtain single plate transmission so far Show the white of netrual colour, show in black display netrual colour black polarizer or polarizer.

Prior art literature

Patent document

Patent document 1：Japanese Patent No. 4281261

Patent document 2：Japanese Patent No. 3357803

Non-patent literature

Non-patent literature 1：

Functional pigmented application (Machine can property pigment ying use) the 1st printing release, Co., Ltd. C MC publishes, and is entering river just Great chief editor, p98-100

The content of the invention

Invent problem to be solved

As the method for the tone for improving polarizer, the technology as patent document 1 or patent document 2 is disclosed.Patent text The polarizer for disclosing that property coefficient and its absolute value are 0~3 in a kind of calculating in 1 is offered, from embodiment, even if middle property coefficient (Np) it is low, but only by just being understood from the point of view of the tone for the parallel position obtained by JIS Z 8729, due to a* values for -2~-1 and B* values are 2.5~4.0, therefore, show yellow green in white displays as color.In addition, the tone on orthogonal position, a* It is worth for 0~1, but b* values are -1.5~-4.0, therefore as showing the polarizer of blueness.Patent Document 2 discloses 410nm ~750nm transmissivity is also adds direct dyes, reactive dye or acid contaminated within ± the 30% of average value, except iodine in addition to The polarizer expected and be prepared into.The polarizer is when making single plate transmission, being measured using only a piece of polarizer Color absolute value is counted as 2 using a values in UCS color spaces, b values within obtained from polarizer, but for using two Tone when piece polarizer carries out white displays (in the case of parallel) and during black display (in the case of orthogonal), it is impossible to simultaneously A values and b values is shown as within 2, netrual colour can not be shown as in orthogonal position peace line position.In addition, observation embodiment is understood, its Single plate transmission is in embodiment 1 31.95%, is 31.41% in example 2, and transmissivity is low, therefore, is requiring high saturating Penetrate the field of rate and high-contrast, be particularly in the fields such as liquid crystal display device, organic electroluminescent, in more high-transmission rate, height It is insufficient in terms of degree of polarization.

The present inventor has made intensive studies to solve above-mentioned problem, as a result new discovery, in order in its parallel position and orthogonal The each position of position makes transmissivity constant and eliminates wavelength dependency and then make the degree of polarization of the parallel position and orthogonal position of each wavelength (dichroic ratio) is constant and has high-polarization and its relation can be also maintained under high-transmission rate, special only by mixture Fixed azo-compound i.e. can be achieved, as a result have developed and can realize high-contrast, show high-transmission rate and high-polarization, The polarizer of netrual colour can be shown in parallel position and orthogonal position.I.e., it was found that：Following single plate transmissions are 35%~45% polarizer, can when the absorption axiss of polarizer are abreast set while with high-transmission rate The white of netrual colour is shown, and the black of netrual colour can be shown when the absorption axiss of polarizer are normally located otherwise Color, the polarizer are characterised by that it is the base material containing iodine and specific azo-compound, on according to JIS Z 8729 The a* values and b* values obtained, a* values and b* values when single plate transmission determines are calculated as within 1 with absolute value, make the two panels base material phase It is calculated as absorbing a* values obtained from direction of principal axis is abreast measured and b* values with absolute value within 2, makes the two panels base material A* values and b* values are calculated as within 2 with absolute value obtained from being orthogonally measured relative to absorption direction of principal axis.

That is, the present invention relates to：

(1) a kind of polarizer, it is the polarizer being made up of the base material containing iodine and azo-compound, the polarizer It is characterised by,

Above-mentioned azo-compound is：A) group of the azo-compound represented by formula (1) and the azo-compound represented by formula (2) Close；Or b) azo-compound represented by formula (1) and the compound represented by the azo-compound represented by formula (3), its The combination of salt or its transition metal complex,

On the a* values and b* values according to calculated by JIS Z 8729, the a* values and b* values when single plate transmission determines are with absolute value It is calculated as within 1, makes the two panels base material relative to absorbing a* values and b* values obtained from direction of principal axis is abreast measured with absolute Value is calculated as within 2, makes the two panels base material relative to absorbing a* values and b* values obtained from direction of principal axis is orthogonally measured with exhausted Value is calculated as within 2,

Single plate transmission is 35%~45%；

【Change 1】

(A₁Represent the phenyl or naphthyl with substituent, R₁Or R₂Hydrogen atom, low alkyl group, rudimentary alcoxyl are represented independently of one another Base, sulfo group or the lower alkoxy with sulfo group, X₁Represent with or without the amino of substituent, with or without substitution The benzoyl-amido of base, the aminobenzoylamino with or without substituent, the benzene with or without substituent Base amino, the phenylazo with or without substituent.)

【Change 2】

(in formula, A₂、A₃The phenyl or naphthyl with substituent is represented independently of one another, and at least one in the substituent is former for hydrogen Son, sulfo group, low alkyl group, lower alkoxy, lower alkoxy, carboxyl, nitro, amino or the substituted-amino with sulfo group, R₃、 R₄Hydrogen atom, low alkyl group, lower alkoxy, sulfo group or the lower alkoxy with sulfo group are represented independently of one another.)

【Change 3】

(in formula, A₄Represent nitro or amino, R₉Represent hydrogen atom, hydroxyl, low alkyl group, lower alkoxy, sulfo group or there is sulphur The lower alkoxy of base, X₂Represent the amino with or without substituent, the phenyl amino with or without substituent.)

(2) polarizer as described in (1), it is characterised in that degree of polarization is more than 99%；

(3) polarizer as described in (1) or (2), it is characterised in that on irradiate the direction of vibration of absolute polarised light relative to The transmissivity of each wavelength when the absorption direction of principal axis of polarizer is the polarised light of orthogonal direction, 550nm~600nm's is average saturating The difference for penetrating rate and 400nm~460nm average transmittance is within 4%, and 600nm~670nm average transmittance with The difference of 550nm~600nm average transmittance is within 3%, moreover, on irradiate the direction of vibration of absolute polarised light relative to The transmissivity of each wavelength when the absorption direction of principal axis of polarizer is the polarised light of parallel direction, 550nm~600nm's is average saturating The difference for penetrating rate and 400nm~460nm average transmittance is within 1%, and 600nm~670nm average transmittance with The difference of 550nm~600nm average transmittance is within 1%；

(4) polarizer as described in (1)~(3), it is characterised in that base material is made up of polyvinyl alcohol resin film；With

(5) a kind of polarizer, it is to set support film to form at least on one side in the polarizer described in (1)~(4)；

(6) a kind of liquid crystal display device, the polarizer described in (1)~(4) or the polarization described in claim 5 are it used Piece.

The effect of invention

The polarizer of the present invention, can when the absorption axiss of polarizer are abreast set while with high-transmission rate The white of netrual colour is shown, and the black of netrual colour can be shown when the absorption axiss of polarizer are normally located otherwise Color.

Embodiment

In the present invention, polarizer is the polarizer that is made up of the base material containing iodine and dichroic dye, the dichroic dye Be made up of specific azo-compound, the polarizer is characterised by, on the a* values according to calculated by JIS Z 8729 and B* values, a* values and b* values when single plate transmission determines are calculated as within 1 with absolute value, make the two panels base material relative to absorption axiss side A* values and b* values are calculated as within 2 with absolute value to obtained from being abreast measured, and make the two panels base material relative to absorption axiss A* values obtained from direction is orthogonally measured and b* values are calculated as within 2 with absolute value, and single plate transmission is 35%~45%. The display methods of object color specified in JIS Z 8729 corresponds to the object of International Commission on Illumination (abbreviation CIE) defined The display methods of color.When single plate transmission represents to determine the transmissivity of its a piece of (monolithic) when irradiating natural light to polarizer Transmissivity, in order that the element is netrual colour, tone during on determining its single plate transmission is, it is necessary to make a* values (with shown below For a*-s) and b* values (being shown as b*-s below) be calculated as with absolute value within 1.In addition, by making two chip bases in incidence natural lights A* values (being shown as a*-p below) and b* values (are shown as b*- below obtained from material is abreast measured relative to absorption direction of principal axis P) it is calculated as with absolute value within 2, also, two plate substrates is orthogonally surveyed relative to direction of principal axis is absorbed in incidence natural lights A* values (being shown as a*-c below) and b* values (being shown as b*-c below) are calculated as within 2 with absolute value obtained from fixed, can be realized Parallel position can show the polarizer of netrual colour.More preferably a*-p and b*-p absolute value is within 1.5 and a*-c and b*-c Absolute value is that further preferred a*-p and b*-p absolute value are within 1.0 and a*-c and b*-c absolute value is within 1.5 Within 1.0.As a*-p and b*-p absolute value, even if absolute value only has 0.5 difference, the susceptibility as people can also be felt Feel the difference of color, therefore it is very important that a* and b*, which are controlled,.Particularly, as the absolute of a*-p and b*-p Value, if monolithic, parallel position and each absolute value of orthogonal position are respectively within 1, turn into white and during black hardly It can confirm that the good polarizer for the degree that color is presented.

Performance as polarizer, it is desirable to which transmissivity is high and degree of polarization is also high.Single plate transmission is if 35%, even if then Brightness, but preferably more than 38%, more preferably more than 39%, more preferably 40% can be also shown for display device More than.As degree of polarization, if more than 99%, polarization function can be just shown as display device, but require contrast more High polarizer, it is desirable to which degree of polarization is more preferably more than 99.9%, more preferably more than 99.95% polarizer.

In order to which the polarizer that single plate transmission is more than 35% is made, (polarizer is characterised by, on according to JIS Z A* values and b* values calculated by 8729, a* values and b* values when single plate transmission determines are calculated as within 1 with absolute value, make two panels should A* values and b* values are calculated as within 2 with absolute value obtained from base material is abreast measured relative to absorption direction of principal axis, make two panels The base material is calculated as within 2 relative to a* values and b* values obtained from direction of principal axis is orthogonally measured is absorbed with absolute value), can be with Realized by the azo-compound for making base material contain iodine and particular combination described later.In the case of containing iodine, using only iodine Sometimes it is difficult to be dissolved in solvent, it is difficult to it is infiltrated up in base material, thus generally with KI, cupric iodide, sodium iodide, calcium iodide etc. The chlorides such as iodide, sodium chloride, lithium chloride, potassium chloride are used together.

Base material is obtained from the material being made up of hydrophilic macromolecule is film-made, and can contain and remember in iodine or non-patent literature 1 The various azo-compounds carried.Hydrophilic macromolecule is not particularly limited, such as has polyvinyl alcohol resin, amylose system tree Fat, starch-series resin, cellulose-based resin, polyacrylate system resin etc..In the case of containing dichroism pigment, from processing Property, dyeability and bridging property etc. set out, most preferably polyvinyl alcohol resin and the resin being made up of its derivative.By these resins Film shape is made, film is contained the dyestuff and its mixed thing of the present invention, using orientation process such as stretchings, thus, it is possible to make polarization Element or polarizer.

The polarizer of the present invention can be by making the azo-compound represented by a) formula (1) and the azo represented by formula (2) The combination of compound；Or b) azo-compound represented by formula (1) and the chemical combination represented by the azo-compound represented by formula (3) Thing, the combination of its salt or its transition metal complex and iodine are infiltrated up in base material and made.Below, to formula (1)~formula (3) institute The azo-compound of expression illustrates.

【Change 4】

In formula (1), A₁Represent the phenyl or naphthyl with substituent, R₁Or R₂Independently of one another represent hydrogen atom, low alkyl group, Lower alkoxy, sulfo group or the lower alkoxy with sulfo group, X₁Represent the amino with or without substituent, have or not Benzoyl-amido with substituent, with or without the aminobenzoylamino of substituent, with or without taking Dai Ji phenyl amino or the phenylazo with or without substituent.X₁Preferably with or without substituent Amino, the benzoyl-amido with or without substituent or the phenyl amino with or without substituent, it is more excellent Select X₁For the phenyl amino with or without substituent, further preferred A₁For the phenyl with substituent, can now obtain The polarizer of the higher the application of degree of polarization, therefore be preferable.It should be noted that the low alkyl group of the application, rudimentary The rudimentary expression carbon number of alkoxy is 1~3.

In formula (1), in A₁In the case of specifically representing the phenyl with substituent, as A₁In phenyl on substitution Base, sulfo group, low alkyl group, lower alkoxy, lower alkoxy, carboxyl, nitro, amino or the substitution with sulfo group can be enumerated Amino.A₁It is preferred that with least one sulfo group as substituent.In addition, in the case of with two or more substituent, it takes One of Dai Ji is sulfo group or carboxyl, is preferably sulfo group, as other substituents, preferably sulfo group, low alkyl group, lower alkoxy, Lower alkoxy, carboxyl, nitro, amino or substituted-amino with sulfo group.It is excellent as the above-mentioned lower alkoxy with sulfo group Select unbranched alkoxy, the more preferably preferred alkoxy end of the position of substitution of sulfo group, 3- sulfo groups propoxyl group, 4- sulfo group butoxy. As above-mentioned substituted-amino, acetyl-amino etc. can be enumerated.In other above-mentioned substituents, more preferably sulfo group, low alkyl group Or lower alkoxy.A₁In phenyl on substitution radix be preferably 1 or 2, be not particularly limited for the position of substitution, preferably 2 Position and the combination of 4.In A₁In the case of representing the naphthyl with substituent, as A₁Substituent in represented naphthyl, no Including hydrogen atom, sulfo group, hydroxyl, amino, substituted-amino, nitro, substituted amido or the carbon atom with sulfo group can be enumerated Number is 1~5 alkoxy, the alkoxy that preferably sulfo group, hydroxyl or the carbon number with sulfo group are 1~5.As A₁It is represented Naphthyl in substituent, preferably with least one sulfo group.In A₁Represented naphthyl has the feelings of two or more substituent Under condition, preferably one of its substituent is sulfo group, and other substituents are selected from by sulfo group, hydroxyl and the carbon number with sulfo group For 1~5 at least one of the group that forms of alkoxy.As the carbon number with sulfo group be 1~5 alkoxy, preferably Carbon number with sulfo group is 1~5 unbranched alkoxy, and the carbon number for more preferably having sulfo group in the end of alkoxy is 1~5 unbranched alkoxy, further preferred 3- sulfo groups propoxyl group or 4- sulfo group butoxy.As A₁Represented naphthyl, preferably The naphthyl substituted by 2 or 3 sulfo groups；Or selected free hydroxyl, 3- sulfo groups propoxyl group and 4- sulfo groups butoxy composition The naphthyl that at least one of group group and 1 or 2 sulfo groups are substituted, the naphthalene more preferably substituted by 2 or 3 sulfo groups Base or the naphthyl substituted by 3- sulfo groups propoxyl group and sulfo group.In addition, according to circumstances, further preferred disulfo naphthyl or Three sulfo group naphthyls, most preferably three sulfo group naphthyls.It is 2 in substituent on preferred the position of substitution of these substituents on naphthalene nucleus It is 1 and 3 in the case of individual, is 1,3 and 6 in the case where substituent is 3.Azo group in the naphthyl The position of substitution is preferably 2.

X₁Specifically represent the amino with or without substituent, the benzoyl-amido with or without substituent, Aminobenzoylamino with or without substituent, with or without substituent phenyl amino or have or Phenylazo without substituent.X₁There can be substituent, for example, it is even in benzoyl-amido, phenyl amino or phenyl In the case of nitrogen base, as its substituent, preferably low alkyl group, lower alkoxy, hydroxyl, carboxyl, sulfo group, amino or substitution ammonia Base, as substituted-amino, acetyl-amino etc. can be enumerated.In X₁For the situation of the phenyl amino with or without substituent Under, its substituent is methyl, methoxyl group, amino, more preferably substituted-amino, preferably acetyl-amino or sulfo group, methyl, methoxy Base or amino.The number and the position of substitution of the substituent on phenyl are not particularly limited.The number of usual substituent is preferably 0 ~2, in the case where the substituent beyond hydrogen be present, a preferably at least substituent exists relative to the binding site of amino In contraposition.As the phenyl amino with or without substituent, for example, phenyl amino, 4- MethYlphenylaminos, 4- Methoxyphenylaminos, 4- aminophenyiaminos, 4- amino -2- sulfo groups phenyl amino, 4- amino -3- sulfo groups phenyl amino, 4- sulfomethvls aminophenyiamino or 4- carboxyethylamino phenyl aminos etc..Among these, more preferably unsubstituted phenyl Amino and p-methoxyphenyl amino.In X₁In the case of for the benzoyl-amido with or without substituent, it is used as Substituent, for the substituted-amino illustrated in amino, acetyl-amino, preferably hydroxyl, more preferably amino and acetyl-amino institute The substituted-amino of illustration, more preferably amino.The number of the substituent on phenyl is usually 0~1, and the position of substitution Being not particularly limited, in the case where the substituent beyond hydrogen atom be present, preferably aligning.In X₁For the feelings of benzoyl-amido Under condition, substitution basis representation hydrogen atom, hydroxyl, amino or substituted-amino, preferably illustrated in hydrogen atom, amino or acetyl-amino Substituted-amino.As the position of substituent, preferably align.As the benzoyl-amido, for example, benzoyl ammonia Base, 4- aminobenzoylaminos, 4- hydroxybenzoylaminos or 4- (3- carboxyl -1- oxopropyls amino) benzoyl ammonia Base, 4- (2- carbomethoxy -1- oxoethylaminos) benzoyl-amido etc..In the benzoyl-amido, more preferably aminobenzene Formylamino.In X₁In the case of for the phenylazo with or without substituent, as its substituent, it can enumerate Alkoxy, amino or the substituted-amino that alkyl that hydroxyl, carbon number are 1~5, carbon number are 1~5, preferably hydroxyl, ammonia Base, methyl, methoxyl group or carboxyl, more preferably hydroxyl.The number of substituent is usually 0~3, is preferably 1~2.As Phenylazo, for example, 2- methylphenylazos base, 3- methylphenylazos base, 2,5- 3,5-dimethylphenyl azos Base, 3- methoxyphenyls azo group, 2- methoxyl group -5- methylphenylazos base, 2,5- Dimethoxyphenyls azo group, 4- amino Phenylazo, 4- hydroxyphenyl azos base or 4- carboxyethylamino phenylazos etc., preferably 4- aminophenyls azo Base, 4- hydroxyphenyl azos base or 4- carboxyethylamino phenylazos.

Then, formula (2) is illustrated.

【Change 5】

In formula (2), A₂、A₃The phenyl or naphthyl with substituent is represented independently of one another, and at least one in the substituent is hydrogen Atom, sulfo group, low alkyl group, lower alkoxy, lower alkoxy, carboxyl, nitro, amino or the substituted-amino with sulfo group, R₃、R₄Hydrogen atom, low alkyl group, lower alkoxy, sulfo group or the lower alkoxy with sulfo group are represented independently of one another.It is preferred that A₂、A₃It is each independently naphthyl, more preferably A₂And A₃It is the naphthyl with sulfo group, further preferred R₃、R₄Independently of one another For lower alkoxy, the polarizer of the higher the application of degree of polarization can be now obtained, therefore is preferable.

Then, formula (3) is illustrated.

【Change 6】

In formula (3), A₄Represent nitro or amino, R₉Represent hydrogen atom, hydroxyl, low alkyl group, lower alkoxy, sulfo group or have The lower alkoxy of sulfo group, X₂Represent the amino with or without substituent, the phenyl amino with or without substituent. It is preferred that A₄For nitro, further preferred R₉For lower alkoxy, the polarization that can now obtain the higher the application of degree of polarization is first Part, therefore be preferable.In addition, the azo-compound of formula (3) can be the form of salt or complex compound, particularly, in order to enter one High performance is walked, transition metal complex obtained from preferably forming complex compound with metals such as copper.

As azo-compound, the azo compounds as color correction can be added using the degree for the performance for not damaging the application Thing.The high azo-compound of particularly preferred dichroism.For example,：Azo-compound shown in non-patent literature 1, C.I. direct Huang 12, C.I. directly Huang 28, C.I. Direct Yellow 44s, C.I. direct oranges 26, C.I. direct oranges 39, C.I. direct oranges 107th, C.I. directly red 2, C.I. directly red 31, C.I. directly red 79, C.I. directly red 81, C.I. directly red 247, C.I. are direct Green 80, C.I. direct greens 59 and Japanese Patent Publication 64-5623, Japanese Unexamined Patent Publication 3-12606, Japanese Unexamined Patent Publication 2001- Azo described in No. 33627 publications, Japanese Unexamined Patent Publication 2002-296417 publications and Japanese Unexamined Patent Application 60-156759 publications Compound etc..Especially it is possible to the azo-compound in trisazo- structure with phenyl J acid is suitably used, particularly more It is preferred that by the azo-compound described in Japanese Unexamined Patent Publication 3-12606 and the azo-compound one of formula (1)~(3) of the present invention With polarizer is used for, further will particularly preferably have the sour Japanese Unexamined Patent Publication 3-12606 of phenyl J in trisazo- structure Azo-compound described in azo-compound with the present invention iodine and the azo-compound of formula (1) and the azo of formula (3) Compound is together used for polarizer.These azo-compounds, can also be with alkali metal in addition to the use in the form of free acid The form of the salt of salt (such as Na salt, K salt, Li salt), ammonium salt or amine uses.But azo-compound is not limited to this, There is dichromatic azo-compound known to can using.By making azo-compound be complexed for free acid, its salt or its copper Salt dyestuff, particularly optical characteristics are improved.One kind can be used only in the azo-compound, can also be with other azo compounds Thing mixture uses, and mixture does not limit.Transmissivity by using such pigment as azo-compound to polarizer It is adjusted, the polarizer that single plate transmission is 35%~45% can be realized, the polarizer is characterised by, on root According to the a* values and b* values calculated by JIS Z 8729, a* values and b* values when single plate transmission determines are calculated as within 1 with absolute value, Make the two panels base material relative to absorb a* values and b* values obtained from direction of principal axis is abreast measured with absolute value be calculated as 2 with It is interior, the two panels base material is calculated as 2 relative to a* values and b* values obtained from direction of principal axis is orthogonally measured is absorbed with absolute value Within.

In order to obtain the polarizer that single plate transmission is more than 35%, (polarizer is characterised by, on according to JIS Z A* values and b* values calculated by 8729, a* values and b* values when single plate transmission determines are calculated as within 1 with absolute value, make two panels should A* values and b* values are calculated as within 2 with absolute value obtained from base material is abreast measured relative to absorption direction of principal axis, make two panels A* values and b* values are calculated as within 2 with absolute value obtained from the base material is orthogonally measured relative to absorption direction of principal axis), pass through The transmissivity of its each wavelength is controlled, can easily be realized.As control method, can easily be realized by following methods： On irradiation substantially 100% polarised light (hereinafter referred to absolute polarised light) direction of vibration relative to base material (polarizer) Each wavelength when absorbing the polarised light that direction of principal axis is orthogonal direction transmissivity, control into 550nm~600nm average transmission The difference of rate and 400nm~460nm average transmittance is within 4% and 600nm~670nm average transmittance and 550nm The difference of~600nm average transmittance is within 3%, moreover, on irradiating the direction of vibration of absolute polarised light relative to base material The transmissivity of each wavelength when the absorption direction of principal axis of polarizer is the polarised light of parallel direction, is adjusted to 550nm~600nm's The difference of average transmittance and 400nm~460nm average transmittance is within 1% and 600nm~670nm average transmission The difference of rate and 550nm~600nm average transmittance is within 1%.

It may further be preferable that each wavelength when being the polarised light of orthogonal direction on the direction of vibration for irradiating absolute polarised light Transmissivity, control into the difference of 550nm~600nm average transmittance and 400nm~460nm average transmittance for 3.5% with The difference of interior and 600nm~670nm average transmittance and 550nm~600nm average transmittance is to be advisable within 2.5%, and And it may further be preferable that each wavelength when being the polarised light of orthogonal direction on the direction of vibration for irradiating absolute polarised light it is saturating Rate is penetrated, the difference for controlling into 550nm~600nm average transmittance and 400nm~460nm average transmittance is within 3.0%, And 600nm~670nm average transmittance and 550nm~600nm average transmittance difference be 2.0% within be advisable.

As the method for the azo-compound represented by the formula that obtains (1), Japanese Unexamined Patent Publication 2003-215338, Japan can be utilized special The method described in flat 9-302250, Japanese Patent No. 3881175 etc. is opened to be made, but not limited to this.As formula (1) institute The concrete example of the azo-compound of expression, for example, C.I. directly red 81, C.I. directly red 117, C.I. are directly red 127th, the azo-compound of the formula described in Japanese Patent No. 3881175 (2), the formula described in Japanese Patent No. 4033443 Etc. (1) dyestuff described in.

As the method for the azo-compound represented by the formula that obtains (2), the side described in such as WO2012/165223 can be utilized Method obtains, but not limited to this.

As the method for the azo-compound represented by the formula that obtains (3), for example, Japanese Unexamined Patent Application 60-156759, Method described in Japanese Unexamined Patent Publication 2-61988, Japanese Patent Application 2011-197600, but not limited to this.

As the more specifically example of the azo-compound represented by formula (1), show that following compound example 1-1~1-15 (is needed It is noted that being represented in the form of free acid).

[compound example 1-1]

【Change 7】

[compound example 1-2]

【Change 8】

[compound example 1-3]

【Change 9】

[compound example 1-4]

【Change 10】

[compound example 1-5]

【Change 11】

[compound example 1-6]

【Change 12】

[compound example 1-7]

【Change 13】

[compound example 1-8]

【Change 14】

[compound example 1-9]

【Change 15】

[compound example 1-10]

【Change 16】

[compound example 1-11]

【Change 17】

[compound example 1-12]

【Change 18】

[compound example 1-13]

【Change 19】

[compound example 1-14]

【Change 20】

[compound example 1-15]

【Change 21】

Then, the more specifically example as the azo-compound represented by formula (2), following compound example 2-1~2-5 is shown (being represented in the form of free acid).

[compound example 2-1]

【Change 22】

[compound example 2-2]

【Change 23】

[compound example 2-3]

【Change 24】

[compound example 2-4]

【Change 25】

[compound example 2-5]

【Change 26】

And then as the more specifically example of the azo-compound represented by formula (3), following compound example 3-1~3- is shown 14 (being represented in the form of free acid).

[compound example 3-1]

【Change 27】

[compound example 3-2]

【Change 28】

[compound example 3-3]

【Change 29】

[compound example 3-4]

【Change 30】

[compound example 3-5]

【Change 31】

[compound example 3-6]

【Change 32】

[compound example 3-7]

【Change 33】

[compound example 3-8]

【Change 34】

[compound example 3-9]

【Change 35】

[compound example 3-10]

【Change 36】

[compound example 3-11]

【Change 37】

[compound example 3-12]

【Change 38】

[compound example 3-13]

【Change 39】

[compound example 3-14]

【Change 40】

Below, as base material, by taking polyvinyl alcohol resin film as an example, the preparation method of specific polarizer is illustrated. The manufacture method of polyvinyl alcohol resin is not particularly limited, and can be made by known method.As manufacture method, example Such as can be by the way that polyvinyl acetate system resin be carried out into saponification to obtain.As polyvinyl acetate system resin, except conduct Beyond the polyvinyl acetate of the homopolymer of vinyl acetate, vinyl acetate can also be exemplified and can be copolymerized with it other Copolymer of monomer etc..As the other monomers with vinyl acetate copolymerization, for example,：Unsaturated carboxylic acid class, alkene Class, vinyl ethers, unsaturated sulfonic acid class etc..The saponification degree of polyvinyl alcohol resin is usually 85 moles of %~100 mole % Left and right, preferably 95 moles of more than %.The polyvinyl alcohol resin can be further modified, such as can also use profit Polyvinyl formal or polyvinyl acetal for being modified with aldehydes etc..In addition, the polymerization of polyvinyl alcohol resin Degree refers to viscometric degree of polymerization, can be obtained by known method in the technical field.Usually 1,000~10,000 is left The right side, it is preferably 1,500~6,000 or so.

The material that polyvinyl alcohol resin film forms uses as base film.The method that polyvinyl alcohol resin is filmed It is not particularly limited, can be filmed by known method.In this case, can contain in polyvinyl alcohol resin film There are glycerine, ethylene glycol, propane diols, low molecular poly etc. to be used as plasticizer.Plasticising dosage is 5wt%~20wt%, excellent Electing 8wt%~15wt% as is advisable.The thickness for the base film being made up of polyvinyl alcohol resin is not particularly limited, for example, 5 μm ~150 μm or so, preferably 10 μm~100 μm or so.

Next to implementing swelling process by base film obtained above.Swelling treatment in 20 DEG C~50 DEG C of solution by soaking Stain is handled for 30 seconds~10 minutes to apply.The preferred water of solution.Stretching ratio is adjusted with 1.00~1.50 times to be advisable, preferably 1.10~1.35 times are advisable.In the case where shortening the time for making polarizer, due to also can in the dyeing processing of pigment It is swelled, therefore swelling treatment can also be omitted.

Process is swelled by making polyvinyl alcohol resin film impregnate 30 seconds~10 minutes in 20 DEG C~50 DEG C of solution to carry out.It is molten The preferred water of liquid.In the case where shortening the time of manufacture polarizer, due to can be also swelled in the dyeing processing of pigment, Therefore swelling process can also be omitted.

After process is swelled, implement dyeing process.In dyeing process, it can use represented by iodine and formula (1)~formula (3) Azo-compound is dyed.For iodine, as long as iodine can be infiltrated up in polyvinyl alcohol resin film, as infiltration Method, the method that iodine, iodide are dissolved in the water and infiltrated is advisable.Iodide can for example use KI, iodine Change ammonium, cobaltous iodide, zinc iodide etc., but be not limited to iodide shown here.Iodine concentration be 0.0001wt%~0.5wt%, Preferably 0.001wt%~0.4wt% is advisable, and iodide concentration is preferably used with 0.0001wt%~8wt%.For non-patent The azo-compound represented by dyestuff or formula (1)~formula (3) described in document 1, can adsorb pigment in dyeing process In polyvinyl alcohol film.Just it is not particularly limited as long as dyeing process makes pigment be adsorbed in the method for polyvinyl alcohol film, for example, it is logical Crossing makes polyvinyl alcohol resin film be immersed in the solution containing dichroic dye to carry out dyeing process.Solution temperature in the process Degree is preferably 5 DEG C~60 DEG C, more preferably 20 DEG C~50 DEG C, particularly preferably 35 DEG C~50 DEG C.The time impregnated in the solution It can moderately adjust, be preferably adjusted with 30 seconds~20 minutes, more preferably 1 minute~10 minutes.Colouring method is preferably to soak Stain, can also be by will carry out in the solution in the solution coating to polyvinyl alcohol resin film.Contain dichroic dye Solution can contain sodium carbonate, sodium acid carbonate, sodium chloride, sodium sulphate, anhydrous sodium sulfate, sodium tripolyphosphate etc. to be helped as dyeing Agent.Their content can be adjusted by the chromatic time based on dyestuff, temperature with arbitrary concentration, as respective Content, preferably 0~5 weight %, more preferably the weight % of 0.1 weight %~2.Contain iodine and azo-compound as film is made Order, can be handled simultaneously, but management from dyeing liquor, productivity ratio etc., preferably make film contain iodine it Colouring method containing azo-compound again afterwards, the method containing iodine again more preferably after making film contain azo-compound.It is even Nitrogen compound is in addition to the use in the form of free acid, or the salt of the compound.Such salt can also with lithium salts, The form of the organic salt such as the alkali metal salt such as sodium salt and sylvite or ammonium salt, alkylamine salt uses.Preferably sodium salt.

After dyeing process, before subsequent processing is entered, matting (hereinafter referred to as matting 1) can be carried out.Scavenger Sequence 1 is the process cleaned to the dye solvent that the surface of polyvinyl alcohol resin film is attached in dyeing process.By entering Row matting 1, dyestuff can be suppressed and be transferred in the follow-up liquid handled.In matting 1, usually using water. Cleaning method is preferably to be immersed in the solution, can also be clear by will be carried out in the solution coating to polyvinyl alcohol resin film Wash.The time of cleaning is not particularly limited, preferably 1 second~300 seconds, more preferably 1 second~60 seconds.It is molten in matting 1 The temperature of agent is needed for the undissolved temperature of hydrophilic macromolecule.Generally cleaning treatment is carried out at 5 DEG C~40 DEG C.But even if There is no the process of matting 1, had no problem in performance yet, therefore this process can also be omitted.

After dyeing process or matting 1, it can enter to exercise the process that film contains crosslinking agent and/or resistance to hydrated agent.As friendship Join agent, can use for example：The polyaldehydes such as the boron compounds such as boric acid, borax or ammonium borate, glyoxal or glutaraldehyde, biuret Titanium sub-group compounds such as the multicomponent isocyanate based compound of type, isocyanurate type or end-sealed type etc., titanyl sulfate etc., except this with Glycol glycidyl ethers, polyamideepichlorohydrin etc. can also be used outside.As resistance to hydrated agent, can enumerate：Peroxidating Butanedioic acid, ammonium persulfate, Calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether, chlorination Ammonium or magnesium chloride etc., preferably using boric acid.Carried out using at least one crosslinking agent above illustrated above and/or resistance to hydrated agent Make the process that film contains crosslinking agent and/or resistance to hydrated agent.As solvent now, preferably water, but do not limit.Film is set to contain friendship The concentration that contains for joining the crosslinking agent in the solvent in the process of agent and/or resistance to hydrated agent and/or resistance to hydrated agent is come by taking boric acid as an example It is the weight % of the weight % of 0.1 weight %~6.0, more preferably 1.0 weight %~4.0 relative to solvent preferred concentration during expression. Solvent temperature in the process is preferably 5 DEG C~70 DEG C, more preferably 5 DEG C~50 DEG C.Make polyvinyl alcohol resin film containing crosslinking The method of agent and/or resistance to hydrated agent is preferably to be immersed in the solution, but by the solution coating or can also be coated to polyethylene On alcohol resin film.Processing time in the process is preferably 30 seconds~6 minutes, more preferably 1 minute~5 minutes.But make film It is not required containing crosslinking agent and/or resistance to hydrated agent, in the case where wanting to shorten the time, does not need crosslinking Treatment or water-fast In the case that change is handled, the treatment process can also be omitted.

After having carried out dyeing process, matting 1 or having made the process that film contains crosslinking agent and/or resistance to hydrated agent, carry out Stretching process.Stretching process is the process that polyvinyl alcohol film is carried out to simple tension.Drawing process can be wet tensile method or Any of dry stretch process, by carrying out the stretching that stretching ratio is more than 3 times, the present invention can be realized.Stretching ratio Carrying out stretching with more than 3 times, preferably 5 times~7 times is advisable.

In the case of dry stretch process, in the case where stretching heating medium is air dielectric, the temperature preferably in air dielectric To be stretched under conditions of normal temperature~180 DEG C.Additionally, it is preferred that handled in the atmosphere that humidity is 20~95%RH.Make For heating means, for example, region pulling method, roller heating pulling method, pressurization pulling method, infrared heating stretching between roller Method etc., but its drawing process does not limit.Stretching process can be stretched with 1 stage, can also be more than the stage more by 2 Stage stretching is carried out.

In the case of wet tensile method, stretched in water, water-miscible organic solvent or its mixed solution.It is preferred that it is being impregnated in Stretch processing is carried out while in solution containing crosslinking agent and/or resistance to hydrated agent.As crosslinking agent, such as boron can be used Polyaldehyde, biuret form, isocyanurate type or the end-blockings such as boron compound, glyoxal or the glutaraldehydes such as acid, borax or ammonium borate Titanium sub-group compounds such as the multicomponent isocyanate based compound of type etc., titanyl sulfate etc., can also be contracted using ethylene glycol in addition Water glycerin ether, polyamideepichlorohydrin etc..As resistance to hydrated agent, can enumerate：Succinic acid peroxide, ammonium persulfate, high chlorine Sour calcium, benzoin ethyl ether, ethylene glycol diglycidylether, glycerin diglycidyl ether, ammonium chloride or magnesium chloride etc..Containing with Shown on it is at least one more than crosslinking agent and/or resistance to hydrated agent solution in stretched.Crosslinking agent preferred boric acid.Stretching The concentration of crosslinking agent and/or resistance to hydrated agent in process is for example preferably the weight % of 0.5 weight %~15, more preferably 2.0 weights Measure the weight % of %~8.0.Stretching ratio is preferably 2 times~8 times, more preferably 5 times~7 times.It is preferred that it is 40 DEG C in draft temperature Handled under conditions of~60 DEG C, more preferably 45 DEG C~58 DEG C.Stretching time is usually 30 seconds~20 minutes, more preferably 2 minutes~5 minutes.Wet tensile process can be stretched with 1 stage, can also be stretched by 2 the multistages more than stage Carry out.

Carry out stretching process after, sometimes crosslinking dose of film surface and/or resistance to hydrated agent precipitation or be attached with foreign matter, therefore, The matting (hereinafter referred to as matting 2) cleaned to film surface can be carried out.Scavenging period is preferably 1 second~5 points Clock.Cleaning method is preferably to be immersed in cleaning solution, but can also by by solution coating or coating to polyvinyl alcohol resin Cleaned on film.Both cleaning treatment can be carried out with 1 stage, 2 multistage the processing more than stage can also be carried out.Cleaning The solution temperature of process is not particularly limited, usually 5 DEG C~50 DEG C, preferably 10 DEG C~40 DEG C.

As the solvent used in treatment process so far, for example,：Water, dimethyl sulfoxide (DMSO), N- methylpyrroles Alkanone, methanol, ethanol, propyl alcohol, isopropanol, glycerine, ethylene glycol, propane diols, diethylene glycol, triethylene glycol, tetraethylene glycol or three The amine equal solvent such as the alcohols such as hydroxymethyl-propane, ethylenediamine or diethylenetriamines, but it is not limited to this.Alternatively, it is also possible to Use the mixture of a kind of the above solvent.Most preferred solvent is water.

After stretching process or matting 2, the drying process of film is carried out.Drying process can be entered by spontaneously drying OK, but in order to further improve drying efficiency, the moisture on surface can be carried out by using the compression of roller, air knife or suction roll etc. Remove, and/or forced air drying can also be carried out.As drying process temperature, place preferably is dried at 20 DEG C~100 DEG C Reason, is more preferably dried processing at 60 DEG C~100 DEG C.The drying process time can apply 30 seconds~20 minutes, preferably 5 points Clock~10 minute.

By the above method, the polarizer that single plate transmission is 35%~45% can be obtained, the polarizer be by containing The polarizer that the base material of iodine and dichroic dye is formed, azo compounds of the dichroic dye represented by formula (1)~formula (3) Thing is formed, and the polarizer is characterised by, on the a* values and b* values according to calculated by JIS Z 8729, single plate transmission is surveyed The a* values and b* values of timing are calculated as within 1 with absolute value, the two panels base material is abreast measured relative to direction of principal axis is absorbed Obtained from a* values and b* values be calculated as with absolute value within 2, the two panels base material is orthogonally surveyed relative to direction of principal axis is absorbed A* values and b* values are calculated as within 2 with absolute value obtained from fixed.

Set protective clear layer that polarizer is made by the single or double in resulting polarizer.Protective clear layer can Set in the form of the coating layer to be formed by polymer or in the form of the layer laminate of film.As formation protective clear layer The transparent polymer or film of transparent polymer or film, preferably high mechanical strength, good thermal stability.As protective clear layer Material, for example,：The acetyl cellulose resins or its film, propylene of triacetyl cellulose or diacetyl cellulose etc Acid resin or its film, Corvic or its film, nylon resin or its film, polyester resin or its film, polyarylate resin or Its film, using the cyclic olefin of ENB etc as the cyclic polyolefin resin of monomer or its film, polyethylene, polypropylene, ring system Polyolefin or polyolefin or its copolymer, the resin that main chain or side chain is acid imide and/or acid amides with ENB skeleton Or polymer or its film etc..In addition, as protective clear layer, can also set with the resin of liquid crystal liquid crystal property or its film.Diaphragm Thickness be, for example, 0.5 μm~200 μm or so.By setting more than 1 layer therein of the same race or not of the same race in single or double The resin or film of class makes polarizer.

Among above-mentioned, in order to which protective clear layer is bonded, it is necessary to bonding agent with polarizer.Do not limited especially as bonding agent Determine, preferably polyvinyl alcohol bonding agent.As polyvinyl alcohol bonding agent, for example,：Gohsenol NH-26 (Japan's synthesis Company manufactures), Exceval RS-2117 (manufacture of KURARAY companies) etc., but be not limited to this.It can be added in bonding agent Crosslinking agent and/or resistance to hydrated agent.Maleic anhydride-isobutylene copolymers are used in polyvinyl alcohol bonding agent, can be made as needed With the bonding agent for being mixed with crosslinking agent.As maleic anhydride-isobutylene copolymers, for example,：Isobam#18 (manufacture of KURARAY companies), Isobam#04 (manufacture of KURARAY companies), ammonia are modified Isobam#104 (KURARAY company systems Make), ammonia be modified Isobam#110 (manufacture of KURARAY companies), imidizate Isobam#304 (manufacture of KURARAY companies), acyl Imidization Isobam#310 (manufacture of KURARAY companies) etc..Crosslinking agent now can use water-soluble polynary epoxide. Water-soluble polynary epoxide for example,：Denacol EX-521 (manufacture of Nagase ChemteX companies), Tetoratto-C (manufacture of three well gas chemical companies) etc..In addition, as the bonding agent beyond polyvinyl alcohol resin, can also Use the known bonding agent of carbamate system, acrylic acid series, epoxy etc.In addition, in order to improve the bonding of bonding agent Power improves water resistance, can also simultaneously with the weight % of 0.1 weight %~10 or so concentration contain zinc compound, chloride, The additives such as iodide.Also do not limited for additive.After using bonding agent, protective clear layer is bonded, in appropriate temperature It is dried or is heat-treated under degree, thus obtains polarizer.

In the situation that resulting polarizer is according to circumstances fitted in the display device such as liquid crystal, organic electroluminescent Under, it can also be provided for improving visual angle on the surface for the protective layer or film for turning into non-exposed surface afterwards and/or improve contrast Various functions layer, have brightness improve property layer or film.It is excellent in order to which polarizer is fitted on these films or display device Choosing uses adhesive.

The polarizer can have anti-reflection layer or antiglare layer, hard painting in the exposed surface of another surface, i.e. protective layer or film Various functions layer known to layer etc..There is the layer of various functions, preferably coating method in order to make this, but can also be by Bonding agent or adhesive are bonded the film with the function.In addition, various functions layer can be made control phase difference layer or Film.

By the above method, polarizer and polarizer that single plate transmission is 35%~45%, the polarizer can be obtained It is characterised by, on the a* values and b* values according to calculated by JIS Z 8729, a* values and b* values when single plate transmission determines Be calculated as with absolute value within 1, make the two panels base material relative to absorb direction of principal axis be abreast measured obtained from a* values and b* Value is calculated as within 2 with absolute value, make the two panels base material relative to absorb direction of principal axis be orthogonally measured obtained from a* values with B* values are calculated as within 2 with absolute value.The polarizer of the present invention or the liquid crystal display device of polarizer has been used to turn into reliability It is high, for a long time with high-contrast and with the liquid crystal display device of high color reprodubility.

So obtained polarizer of the invention or polarizer are arranged as required to protective layer or functional layer and supporter etc., For liquid crystal projection apparatus, calculator, clock and watch, notebook computer, word processor, liquid crystal TV set, spreadlight lens, polarisation eye Mirror, the measuring instrument of automatic navigator and indoor and outdoor or display instrument etc..Particularly in reflection-type liquid-crystal display device, half transmitting liquid It is used as effective polarizer or polarizer in crystal device, organic electroluminescent etc..

As the application process of the polarizer of the present invention, can be used in the form of the polarizer with supporter.In order to paste partially Shake piece, and supporter preferably has planar portions, further, since be optical applications, thus preferably glass molded article.As glass into Shape product, for example, glass plate, lens, prism (such as triangular prism, block prism) etc..Polarization is pasted with lens Piece person may be used as the collector lens with polarizer in liquid crystal projection apparatus.In addition, the person that is pasted with polarizer on prism is in liquid The polarisation spectroscope with polarizer or the dichroic prism with polarizer are may be used as in brilliant projecting apparatus.Alternatively, it is also possible to be pasted on On liquid crystal cells.As the material of glass, formed for example, soda-lime glass, borosilicate glass, by crystal inorganic The modeling of the organic systems such as the glass or acrylic resin, makrolon of the inorganic systems such as substrate, the inorganic substrate being made up of sapphire Flitch, the glass of preferably inorganic system.The thickness and size of glass plate can be desired size.In addition, in order to further carry High single plate transmission, the polarizer with glass preferably set AR layers on the single or double during its glass surface or polarization are unilateral. On such supporter, such as transparent bonding (bonding) agent is coated with supporter planar portions, is then pasted in the coated face The polarizer of the present invention.Alternatively, it is also possible to be coated with transparent bonding (bonding) agent on polarizer, then glued on the coated face Paste supporter.Bonding (bonding) agent of bonding (bonding) agent such as preferred acrylate system used herein.It should be noted that In the case where the polarizer is used as into ellipsoidal polarizing plate, polarizer side is generally pasted onto support side, but can also incite somebody to action Polarizer side is affixed on glass molded article.

Embodiment

Below, by embodiment, the present invention will be described in more detail, but the present invention and is not limited to the examples restriction.Need It is noted that the evaluation of the transmissivity shown in embodiment is carried out as follows.

The transmissivity of each wavelength when being measured with a piece of polarizer or polarizer is set to transmissivity Ts, two panels will be made inclined Shake element or polarizer it is overlapping in a manner of it absorbs direction of principal axis identical when the transmissivity of each wavelength be set to parallel position transmissivity Tp, the transmissivity of each wavelength of two panels polarizer when overlapping in a manner of its absorption axis is orthogonal is set to orthogonal position transmissivity Tc, The single plate transmission that visibility correction has been carried out using 2 ° of visual field color matching functions of illuminant-C is set to Ys, will be through visibility school Parallel transmission after just is set to Yp, and the orthogonal transmission after visibility corrects is set into Yc, utilizes spectrophotometer [Hitachi " U-4100 " of manufacturing company's manufacture] it is measured with 5nm intervals, calculated using its measured value.On polarizer Or the tone of polarizer, by by JIS Z8729 (method for expressing L*, a*, b* colorimeter system of color and L*, u*, v* colourity system System) shown in colorimeter system, using spectrophotometer U-4100 determine tone a* and b*, use its measured value.It is described herein The tone of orthogonal position refer to, by two panels polarizer by absorption axiss it is each it is self-orthogonal in a manner of it is overlapping in the state of be measured when The tone showed, the tone of parallel position refer to, by two panels polarizer by absorption axiss it is each it is autoparallel in a manner of overlapping shape The tone showed when being measured under state.In L*, a*, b* colorimeter system, a*, b* each closer to zero, represent tone More show muted color.Generally, a* values are that timing shows red color tone, and to show green when bearing, b* is that timing shows Huang Tone, to show blue cast when bearing.

Degree of polarization Py utilizes the parallel position transmissivity Yp after visibility corrects and the orthogonal position transmissivity after visibility corrects Yc is obtained by following formula.

Py={ (Yp-Yc)/(Yp+Yc) }^1/2×100

And then determined using spectrophotometer [company of Hitachi manufactures " U-4100 "] saturating when irradiating absolute polarised light Penetrate rate.When determining transmissivity, set in the exiting side of light and visibility correction is carried out based on JIS Z 8729 (2 ° of visuals field of illuminant-C) The iodine system polarizer (Polatechno companies manufacture SKN-18043P) that transmissivity afterwards is 43%, degree of polarization is 99.99% is made For absolute polarizer, absolute polarised light is set to incide measure sample.The application's during the incident absolute polarised light of measure is inclined Shake the parallel position of element and the transmissivity of orthogonal position.SKN-18043P protective layer is the triacetyl of no ultraviolet absorption ability Cellulose.

By the absorption axiss of absorption axiss and the absolute polarizer of the polarizer for making the present invention abreast incident absolute polarised light when determine The absolute parallel transmissivity of obtained each wavelength is set to Ky, will make absorption axiss and the suction of absolute polarizer of the polarizer of the present invention Receive axle orthogonally incident absolute polarised light when the absolute orthogonal transmission of each wavelength that determines to obtain be set to Kz, determine each wavelength Ky and Kz.

Made using the combination of the azo-compound represented by above-mentioned formula (1) and the azo-compound represented by above-mentioned formula (2) The polarizer of the present invention, shows the result in embodiment 1~4.

Embodiment 1

The polyvinyl alcohol film for being 2400 by the average degree of polymerization that saponification degree is more than 99% (KURARAY companies manufacture VF-PS) exists Impregnated 2 minutes in 45 DEG C of warm water, using swelling treatment, it is 1.30 times to make stretching ratio.By the film after swelling treatment containing The parts by weight of water 1500, the parts by weight of sodium tripolyphosphate 1.5, structure with formula (1) C.I. directly red 810.1 parts by weight, with Soaked in the aqueous solution of the regulation to 45 DEG C of the parts by weight of dyestuff 0.85 shown in the WO2012/165223 synthesis 2 of the structure of formula (2) Stain 3 is divided 30 seconds, and resulting film is utilized and contains boric acid (manufacture of Societa chimica lardrello s.p.a companies) 28.6g/l, iodine (pure chemical company's manufacture) 0.25g/l, KI (pure chemical company's manufacture) 17.7g/l, ammonium iodide are (pure Just chemical company system is made) the 1.0g/l aqueous solution impregnates 2 minutes at 30 DEG C, make its contain iodine, iodide and dyed.Should The film obtained after dyeing is stretched to 5.0 times while being carried out in the aqueous solution of 50 DEG C containing boric acid 30.0g/l 5 minutes Stretch processing.The tense situation of film obtained after boric acid processing is kept, while in the aqueous solution for being adjusted to KI 20g/l 30 DEG C are held in while handle within 20 seconds.The film that processing obtains is subjected to drying process in 9 minutes at 70 DEG C, obtains this hair Bright polarizer.

Embodiment 2

C.I. described in embodiment 1 directly red 81 0.1 parts by weight are changed to the Japanese Patent No. with the structure of formula (1) The parts by weight of azo-compound 0.07 described in 2003-215338 synthesis examples 1, similarly make polarizer in addition, system Into measure sample.

Embodiment 3

In example 2, the time that polyvinyl alcohol film contains azo-compound will be made to be changed within 30 seconds 3 points 00 second from 3 points, using containing There are boric acid (manufacture of Societa chimica lardrello s.p.a companies) 28.6g/l, iodine (pure chemical company's manufacture) 0.25g/l, KI (pure chemical company manufacture) 17.7g/l, ammonium iodide (pure chemical company's manufacture) 1.0g/l it is water-soluble Liquid 30 DEG C dipping 1 point 30 seconds, make its contain iodine, iodide and dyed, similarly make polarizer in addition, make Into measure sample.

Embodiment 4

In example 2, as the azo-compound for making polyvinyl alcohol film contain azo-compound, with the structure with formula (1) Japanese Patent No. 2003-215338 synthesis examples 1 described in the parts by weight of azo-compound 0.07 and structure with formula (2) The parts by weight of dyestuff 0.85 shown in WO2012/165223 synthesis 2 together add the day in trisazo- structure with phenyl J acid The parts by weight of azo-compound 0.08 described in this Unexamined Patent 3-12606 embodiments 1, polarization member is similarly made in addition Part, measure sample is made.

Comparative example 1

Iodine system polarizer without dichroic dye has been made according to the formula of Japanese Unexamined Patent Publication 2008-065222 comparative examples 1, removed Measure sample is made similarly to Example 1 beyond this.

Comparative example 2

The only polarizer containing dichroic dye has been made according to the method for Japanese Unexamined Patent Publication 11-218611 embodiments 1, except this with Polarizer is made similarly to Example 1 outside, and measure sample is made.

Comparative example 3

Dyestuff system polarizer only containing dichroic dye has been made according to the method for the embodiment 3 of Japanese Patent No. 4162334, removed Polarizer is made similarly to Example 1 beyond this, and measure sample is made.

Comparative example 4

Dyestuff system polarizer only containing dichroic dye has been made according to the method for the embodiment 1 of Japanese Patent No. 4360100, removed Polarizer is made similarly to Example 1 beyond this, and measure sample is made.

The measurement result of Ys, ρ, a*-s, b*-s, a*-p, b*-p, a*-c, b*-c in embodiment 1~4, comparative example 1~4 are shown In table 1.

【Table 1】

The average transmission of 400nm~460nm when showing the incident absolute polarised light of embodiment 1~4 and comparative example 1~4 in table 2 Rate, 550nm~600nm average transmittance, 600nm~670nm average transmittance and 400nm~460nm it is average saturating Penetrate the absolute value of difference, 550nm~600nm average transmittance and the 600nm of rate and 550nm~600nm average transmittance~ The absolute value of the difference of 670nm average transmittance.

【Table 2】

In addition, for the polarizer being dried to obtain, tri acetyl cellulose membrane (the Fuji Photo Film Co., Ltd.'s system that alkali process will be carried out Make TD-80U) protective clear layer is used as, it is laminated using polyethenol series bonding agent and polarizer is made, even so, should Each optical characteristics of polarizer does not also change.Thus will also realize that, the polarizer obtained using the polarizer is similarly With equal performance.

Then, using the combination system of the azo-compound represented by above-mentioned formula (1) and the azo-compound represented by above-mentioned formula (3) Make the polarizer of the present invention, show the result in embodiment 5~9.

Embodiment 5

The polyvinyl alcohol film for being 2400 by the average degree of polymerization that saponification degree is more than 99% (KURARAY companies manufacture VF-PS) exists Impregnated 2 minutes in 45 DEG C of warm water, using swelling treatment, it is 1.30 times to make stretching ratio.By the film after swelling treatment containing The parts by weight of water 1500, the parts by weight of sodium tripolyphosphate 1.5, structure with formula (1) C.I. directly red 81 0.1 parts by weight, with The regulation of the parts by weight of dyestuff 0.135 shown in the Japanese Patent Publication 2-61988 embodiments 3 of the structure of formula (3) is to 45 DEG C 3 points are impregnated in the aqueous solution 30 seconds, resulting film is utilized and contains boric acid (Societa chimica lardrello s.p.a Company manufactures) 28.6g/l, iodine (pure chemical company manufacture) 0.25g/l, KI (pure chemical company's manufacture) 17.7g/l, Ammonium iodide (pure chemical company manufacture) 1.0g/l aqueous solution impregnates 2 minutes at 30 DEG C, make its contain iodine, iodide and carry out Dyeing.The film obtained after this is dyed is stretched to 5.0 times while entering in the aqueous solution of 50 DEG C containing boric acid 30.0g/l The row stretch processing of 5 minutes.The tense situation of film obtained after boric acid processing is kept, while is being adjusted to KI 20g/l The aqueous solution in be held in 30 DEG C while carry out 20 seconds handle.Obtained film will be handled at 70 DEG C of progress drying in 9 minutes Reason, obtain the polarizer of the present invention.For the polarizer being dried to obtain, carried out using the stacking of polyethenol series bonding agent The tri acetyl cellulose membrane (Fuji Photo Film Co., Ltd. manufacture TD-80U) of alkali process and obtain polarizer.Resulting polarizer is cut 40mm × 40mm is cut into, is bonded by adhesive PTR-3000 (Japanese chemical drug company system is made) with 1mm glass plate, measure is made Sample.

Embodiment 6

C.I. described in embodiment 5 directly red 81 0.1 parts by weight are changed to the Japanese Patent No. with the structure of formula (1) The parts by weight of azo-compound 0.07 described in 2003-215338 synthesis examples 1, in addition similarly make polarizer and partially Shake piece, and measure sample is made.

Embodiment 7

In embodiment 6, the time that polyvinyl alcohol film contains azo-compound will be made to be changed within 30 seconds 3 points 00 second from 3 points, using containing There are boric acid (manufacture of Societa chimica lardrello s.p.a companies) 28.6g/l, iodine (pure chemical company's manufacture) 0.25g/l, KI (pure chemical company manufacture) 17.7g/l, ammonium iodide (pure chemical company's manufacture) 1.0g/l it is water-soluble Liquid 30 DEG C dipping 1 point 30 seconds, make its contain iodine, iodide and dyed, in addition similarly make polarizer and Polarizer, measure sample is made.

Embodiment 8

In embodiment 6, as the azo-compound for making polyvinyl alcohol film contain azo-compound, with the structure with formula (1) Japanese Patent No. 2003-215338 synthesis examples 1 described in the parts by weight of azo-compound 0.07 and structure with formula (3) The parts by weight of dyestuff 0.135 shown in Japanese Patent Publication 2-61988 embodiments 3 together add Japanese Unexamined Patent Publication 3-12606 The parts by weight of azo-compound 0.08 described in embodiment 1, polarizer and polarizer are similarly made in addition, survey is made Determine sample.

Embodiment 9

By the dyestuff shown in the Japanese Patent Publication 2-61988 embodiments 3 of the structure with formula (3) used in embodiment 6 0.135 parts by weight are changed to the azo for having described in the Japanese Patent Publication 60-156759 embodiments 24 of the structure of formula (3) The parts by weight of compound 0.155, polarizer and polarizer are similarly made in addition, measure sample is made.

Comparative example 5~8

Using manufactured polarizer in above-mentioned comparative example 1~4, polarizer is made in the same manner as above-described embodiment 5, measure is made Sample.

The measurement result of Ys, ρ, a*-s, b*-s, a*-p, b*-p, a*-c, b*-c in embodiment 5~9, comparative example 5~8 are shown In table 3.

【Table 3】

The average transmission of 400nm~460nm when showing the incident absolute polarised light of embodiment 5~9 and comparative example 5~8 in table 4 Rate, 550nm~600nm average transmittance, 600nm~670nm average transmittance and 400nm~460nm it is average saturating Penetrate the absolute value of difference, 550nm~600nm average transmittance and the 600nm of rate and 550nm~600nm average transmittance~ The absolute value of the difference of 670nm average transmittance.

【Table 4】

Observe in the embodiment 1~4 shown in table 1 and the embodiment 5~9 and comparative example 5~8 shown in comparative example 1~4, table 3 Ys, ρ, a*-s, b*-s, a*-p, b*-p, a*-c, b*-c measurement result understand that polarizer of the invention is that single plate transmission is 35%~45% polarizer, it is characterised in that on the a* values and b* values of the defineds of JIS Z 8729, single plate transmission is surveyed The a* values and b* values of timing are calculated as within 1 with absolute value, the two panels base material is abreast measured relative to direction of principal axis is absorbed Obtained from a* values and b* values be calculated as with absolute value within 2, the two panels base material is orthogonally surveyed relative to direction of principal axis is absorbed A* values and b* values are calculated as within 2 with absolute value obtained from fixed, by polarizer as acquisition or polarizer, in parallel position White displays and orthogonal position black display when it is each in the case of show the white and black of netrual colour.On 410nm~ 750nm average transmittance, it is known that polarizer of the invention and polarizer also have the Japan Patent for being used for prior art The higher transmissivity of about 31%~32% polarizer described in the embodiment 1 or 2 of No. 3357803 (patent document 2).Separately Outside, when average transmittance is more than 40%, L values (L*) have obtained quite good polarizer also above 70.It is it is said that logical Crossing makes the tone of color medium be within ± 1.0 and L* is more than 65, it becomes possible to white as the good paper of quality is realized, and L* reaches To 70, the polarizer of white, i.e. so-called paper white as can realizing the paper of high-quality resulting in.

In addition, as shown in table 2 and table 4, understood when being compared to the transmissivity of each wavelength, the polarizer of embodiment 1~9 and Polarizer is the polarizer for having carried out following adjustment：Direction of vibration on irradiating absolute polarised light polarizes member relative to base material Part absorb direction of principal axis be orthogonal direction polarised light when each wavelength transmissivity, 550nm~600nm average transmittance with The difference of 400nm~460nm average transmittance is within 4%, and 600nm~670nm average transmittance and 550nm~ The difference of 600nm average transmittance is within 3%, moreover, inclined relative to base material on the direction of vibration for irradiating absolute polarised light Shake element absorb direction of principal axis be parallel direction polarised light when each wavelength transmissivity, 550nm~600nm average transmission The difference of rate and 400nm~460nm average transmittance is and 600nm~670nm average transmittance and 550nm within 1% The difference of~600nm average transmittance is within 1%.The polarizer obtained using the polarizer is with the same of high-transmission rate When, it can show the white of netrual colour when the absorption axiss of polarizer are abreast set, and by the absorption of polarizer Axle can show the black of netrual colour when being normally located otherwise.Therefore, the polarizer of the present invention or the liquid of polarizer have been used Crystal device, which turns into, not only has high brightness, high-contrast, and reliability it is high, for a long time with high-contrast and with The liquid crystal display device of high color reprodubility.

Claims

1. a kind of polarizer, it is the polarizer being made up of the base material containing iodine and azo-compound, the polarizer It is characterised by,

The azo-compound is：A) group of the azo-compound represented by formula (1) and the azo-compound represented by formula (2) Close；Or b) azo-compound represented by formula (1) and the compound represented by the azo-compound represented by formula (3), its The combination of salt or its transition metal complex,

Single plate transmission is 35%~45%,

【Change 1】

A₁Represent the phenyl or naphthyl with substituent, R₁Or R₂Hydrogen atom, low alkyl group, rudimentary alcoxyl are represented independently of one another Base, sulfo group or the lower alkoxy with sulfo group, X₁Represent with or without the amino of substituent, with or without substitution The benzoyl-amido of base, the aminobenzoylamino with or without substituent, the benzene with or without substituent Base amino, the phenylazo with or without substituent,

【Change 2】

In formula, A₂、A₃The phenyl or naphthyl with substituent is represented independently of one another, and at least one in the substituent is former for hydrogen Son, sulfo group, low alkyl group, lower alkoxy, lower alkoxy, carboxyl, nitro, amino or the substituted-amino with sulfo group, R₃、 R₄Hydrogen atom, low alkyl group, lower alkoxy, sulfo group or the lower alkoxy with sulfo group are represented independently of one another,

【Change 3】

In formula, A₄Represent nitro or amino, R₉Represent hydrogen atom, hydroxyl, low alkyl group, lower alkoxy, sulfo group or there is sulfo group Lower alkoxy, X₂Represent the amino with or without substituent, the phenyl amino with or without substituent.

2. polarizer as claimed in claim 1, it is characterised in that degree of polarization is more than 99%.

3. polarizer as claimed in claim 1 or 2, it is characterised in that

Direction of vibration on irradiating absolute polarised light absorbs the polarised light that direction of principal axis is orthogonal direction relative to polarizer When each wavelength transmissivity, the difference of 550nm~600nm average transmittance and 400nm~460nm average transmittance is Within 4%, and the difference of 600nm~670nm average transmittance and 550nm~600nm average transmittance be 3% within,

Moreover, direction of principal axis is absorbed for the inclined of parallel direction relative to polarizer on the direction of vibration for irradiating absolute polarised light Shake light when each wavelength transmissivity, the difference of 550nm~600nm average transmittance and 400nm~460nm average transmittance Within 1%, and the difference of 600nm~670nm average transmittance and 550nm~600nm average transmittance be 1% with It is interior.

4. the polarizer as described in claims 1 to 3, it is characterised in that base material is made up of polyvinyl alcohol resin film.

5. a kind of polarizer, its be protective clear layer is set at least on one side in the polarizer described in Claims 1 to 4 and Into.

6. a kind of liquid crystal display device, it use inclined described in polarizer or the claim 5 described in Claims 1 to 4 Shake piece.