WO2018079651A1 - 偏光素子、並びにこれを用いた偏光板及び液晶表示装置 - Google Patents
偏光素子、並びにこれを用いた偏光板及び液晶表示装置 Download PDFInfo
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- WO2018079651A1 WO2018079651A1 PCT/JP2017/038698 JP2017038698W WO2018079651A1 WO 2018079651 A1 WO2018079651 A1 WO 2018079651A1 JP 2017038698 W JP2017038698 W JP 2017038698W WO 2018079651 A1 WO2018079651 A1 WO 2018079651A1
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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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a dye-type polarizing element, a polarizing plate using the same, and a liquid crystal display device.
- a polarizing element is generally produced by adsorbing and orienting iodine or dichroic dye, which is a dichroic dye, on a polyvinyl alcohol resin film.
- a polarizing plate obtained by bonding a protective film made of triacetyl cellulose or the like to this polarizing element via an adhesive layer is used for a liquid crystal display device or the like.
- a polarizing plate using iodine as a dichroic dye is called an iodine polarizing plate, while a polarizing plate using a dichroic dye, for example, an azo compound having dichroism, is a dye-based polarizing plate. Called.
- the dye-based polarizing plate has high heat resistance, high heat and humidity resistance, and high stability, and has the same degree of polarization while being characterized by high color selectivity due to the combination of pigments.
- the transmittance and contrast were low as compared with the iodine-based polarizing plate. Therefore, there is a demand for a polarizing element having high polarization characteristics with higher transmittance in addition to maintaining high durability and various color selectivity.
- the conventional polarizing elements have a positional relationship in which the absorption axis directions of the two polarizing elements are parallel to each other (hereinafter also referred to as “parallel position”).
- the white color is displayed so as to overlap (hereinafter also referred to as “white display” or “bright display”), the white has a yellowish white color.
- the conventional polarizing plate has a low degree of polarization or contrast, and is extremely durable. There was a problem that it was low.
- An iodine polarizing plate will be described as an example.
- An iodine polarizing plate using polyvinyl alcohol (hereinafter also referred to as “PVA”) as a base material and iodine as a dichroic dye is generally 480 nm and 600 nm. Absorption centered on The absorption at 480 nm is said to be due to the complex of polyiodine I 3 — and PVA, and the absorption at 600 nm is said to be due to the complex of polyiodine I 5 — and PVA.
- PVA polyvinyl alcohol
- the degree of polarization (dichroism) at each wavelength is such that the degree of polarization (dichroism) based on the complex of polyiodine I 5 - and PVA is the degree of polarization based on the complex of polyiodine I 3 - and PVA ( Higher than dichroic). That is, if the orthogonal transmittance is made constant at each wavelength, the parallel transmittance is higher at 600 nm than at 480 nm, and a phenomenon occurs in which white is colored yellow during white display. On the other hand, if the parallel transmittance is made constant, the orthogonal transmittance becomes lower at 600 nm than at 480 nm, so that black is colored blue during black display and the contrast is greatly reduced.
- an iodine-type polarizing plate having a constant parallel transmittance is significantly lower in durability than a black-oriented polarizing plate when orthogonal. This indicates that although the polarizing plate having iodine in general has low durability, the polarizing plate having a constant parallel transmittance is further low in durability.
- white yellow when white is displayed, it is generally not preferable because it gives an impression that the deterioration has progressed.
- a blue color is lost during black display, it is not clear black and gives an impression that there is no sense of quality, the contrast is lowered, and the durability is remarkably lowered.
- the hue cannot be adjusted with an iodine polarizing plate made of iodine and PVA.
- Patent Document 1 describes a polarizing plate that calculates a neutral coefficient and has an absolute value of 0 to 3.
- Patent Document 2 describes a polarizing film obtained by adjusting the transmittance at 410 nm to 750 nm within ⁇ 30% of the average value and adjusting the color by adding a direct dye, a reactive dye, or an acid dye in addition to iodine. Has been.
- JP 2002-169024 A JP-A-10-1333016 WO2014 / 162635
- the parallel hue obtained from JIS Z 8729 has an a * value of ⁇ 2 to ⁇ 1, and , B * value is from 2.5 to 4.0, and it can be seen that yellowish green is displayed during white display.
- the a * value is 0 to 1 in the orthogonal hue
- the b * value is ⁇ 1.5 to ⁇ 4.0, so that the black display is a polarizing plate exhibiting a blue color. ing.
- the polarizing film of Patent Document 2 is obtained by setting the a value and b value in the UCS color space measured using only one polarizing film to an absolute value of 2 or less, and two polarizing films are stacked.
- the achromatic color cannot be expressed at the same time in both the white display and the black display, and the contrast is very low.
- the average value of the single transmittance of the polarizing film of Patent Document 2 was 31.95% in Example 1 and 31.41% in Example 2, indicating a low value.
- the polarizing film of Patent Document 2 since the polarizing film of Patent Document 2 has low transmittance, the polarizing film does not have sufficient performance in fields where high transmittance and high contrast are required, particularly in fields such as liquid crystal display devices and organic electroluminescence. .
- the polarizing film of Patent Document 2 uses iodine as the main dichroic dye, the color after the durability test, particularly after the wet heat durability test (for example, an environment of 85 ° C. and a relative humidity of 85%). The change was great and the durability was poor.
- the dye-based polarizing plate is excellent in durability, but the wavelength dependency is different between the parallel position and the orthogonal position, similarly to the iodine-based polarizing plate. Almost no azo compounds exhibiting dichroism exhibiting the same hue in parallel and orthogonal positions, and even if they exist, the contrast (or degree of polarization) is low. Depending on the type of azo compound having dichroism, the white color at the time of white display is yellow, the black color at the time of black display is blue, and the contrast is lowered. There are many azo compounds.
- Patent Document 3 also describes an achromatic polarizing plate during white display and black display, but further improvement in performance is desired.
- an object of the present invention is to provide a high-performance polarizing element that exhibits a paper white color during white display and has high transmittance and high contrast, and a polarizing plate and a liquid crystal display device using the same.
- the present inventor has produced a high-performance polarizing element that exhibits a high transmittance and a paper white color at the time of white display and a high contrast by blending a specific azo compound. Found to get.
- the present inventor has found for the first time that wavelength independence in the visible light region can be achieved even with high transmittance, and it is higher than that which can realize white, commonly known as paper white, such as high-quality paper.
- a polarizing element having a degree of polarization was developed.
- [Invention 1] A polarizing element comprising an azo compound represented by formula (1a) or (1b) or a salt thereof and an azo compound represented by formula (2) or a salt thereof.
- Ar 1 represents a phenyl group or naphthyl group having at least one substituent
- Rr 1 to Rr 4 each independently represents a lower group having a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a sulfo group.
- Av 1 represents a phenyl group or a naphthyl group having at least one substituent selected from a sulfo group and a carboxy group
- Rv 1 to Rv 6 each independently represents a hydrogen atom or a lower alkyl group.
- An amino group, a phenylamino group, a phenylazo group, a naphthotriazole group, or a benzoylamino group which may have at least one substituent selected from the group consisting of (In the formula, Ag 1 represents a phenyl group or a naphthyl group having a substituent, and Bg and Cg are each independently represented by the formula (BC-N) or the formula (BC-P), and at least one of the formula (BC-P) BC-N), and Xg 1 has an amino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a substituent.
- Rg 1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy group having a sulfo group
- k represents an integer of 0 to 2.
- Rg 2 and Rg 3 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy group having a sulfo group.
- the polarizing element according to invention 1 comprising both at least one compound represented by formula (1a) or a salt thereof and at least one compound represented by formula (1b) or a salt thereof.
- Ay 1 represents a sulfo group, a carboxy group, a hydroxy group, a lower alkyl group, or a lower alkoxy group
- Ry 1 to Ry 4 each independently represents a hydrogen atom, a sulfo group, a lower alkyl group, or a lower group. Represents an alkoxy group
- p represents an integer of 1 to 3.
- the single transmittance of the polarizing element is 35% to 65%, The average transmittance of 520 nm to 590 nm obtained in a state where the two polarizing elements are stacked and arranged so that the absorption axis directions thereof are parallel to each other is 25% to 45%.
- invention 10 A polarizing plate comprising the polarizing element according to any one of inventions 1 to 9 and a transparent protective layer provided on one or both sides of the polarizing element.
- invention 11 A liquid crystal display device comprising the polarizing element according to any one of Inventions 1 to 9 or the polarizing plate according to Invention 10.
- the present invention can provide a high-performance polarizing element that exhibits a paper white color during white display and has high transmittance and high contrast, and a polarizing plate and a liquid crystal display device using the same.
- the polarizing element according to the present invention contains an azo compound represented by formula (1a) or (1b) and an azo compound represented by formula (2).
- both the azo compound represented by the formula (1a) and the azo compound represented by (1b) may be contained.
- an azo compound represented by the formula (3) may be further contained.
- the polarizing element includes these azo compounds or salts thereof and a substrate on which the azo compounds or salts thereof are adsorbed.
- the base material is preferably a film obtained by forming a hydrophilic polymer capable of adsorbing a dichroic dye, particularly an azo compound.
- the hydrophilic polymer is not particularly limited, and examples thereof include polyvinyl alcohol resins, amylose resins, starch resins, cellulose resins, polyacrylate resins, and derivatives thereof.
- the hydrophilic polymer is most preferably a polyvinyl alcohol-based resin and derivatives thereof from the viewpoints of dyeability, processability and crosslinkability of the dichroic dye.
- a polarizing element can be produced by adsorbing an azo compound or a salt thereof to a substrate and applying an alignment treatment such as stretching.
- Ar 1 represents a phenyl group or naphthyl group having at least one substituent
- Rr 1 to Rr 4 each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a sulfo group. Represents a lower alkoxy group.
- “lower” means having 1 to 4 carbon atoms.
- a lower alkyl group means an alkyl group having 1 to 4 carbon atoms.
- Ar 1 when Ar 1 is a phenyl group, it preferably has at least one substituent selected from a sulfo group, a carboxy group, and an alkoxy group, and is selected from a sulfo group and a carboxy group. More preferably, it has at least one substituent.
- the phenyl group has two or more substituents, at least one of the substituents is a sulfo group or a carboxy group, and the other substituents are preferably a sulfo group, a carboxy group, a lower alkyl group, a lower alkoxy group.
- the lower alkoxy group having a sulfo group is preferably a linear alkoxy group, and the substitution position of the sulfo group is preferably the terminal of the alkoxy group.
- Such a lower alkoxy group having a sulfo group is more preferably a 3-sulfopropoxy group or a 4-sulfobutoxy group, and particularly preferably a 3-sulfopropoxy group.
- the number of sulfo groups is preferably 1 or 2, and the substitution position of the sulfo group is not particularly limited. In the case of two, the 4-position of the phenyl group is preferred, and when the number of sulfo groups is 2, the combination of the 2-position and 4-position of the phenyl group, or the combination of the 3-position and 5-position of the phenyl group is preferred.
- Ar 1 when Ar 1 is a naphthyl group, it preferably has at least one sulfo group as a substituent.
- the naphthyl group has two or more substituents, at least one of the substituents is a sulfo group, and the other substituents are preferably lower groups having a sulfo group, a hydroxy group, a carboxy group, and a sulfo group. Selected from the group consisting of alkoxy groups.
- the lower alkoxy group having a sulfo group is preferably a linear alkoxy group, and the substitution position of the sulfo group is preferably the terminal of the alkoxy group.
- Such a lower alkoxy group having a sulfo group is more preferably a 3-sulfopropoxy group or a 4-sulfobutoxy group, and particularly preferably a 3-sulfopropoxy group.
- the substitution position of the sulfo group is the 4-position, 8-position combination or 6-position of the naphthyl group, A combination at the 8th position is preferable, and a combination at the 6th and 8th positions is more preferable.
- the substitution position of the sulfo group is preferably a combination of the 3rd, 6th and 8th positions.
- Rr 1 to Rr 4 each independently represents a lower alkoxy group having a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a sulfo group.
- the lower alkoxy group having a sulfo group is preferably a linear alkoxy group, and the substitution position of the sulfo group is preferably the terminal of the alkoxy group.
- Rr 1 to Rr 4 are preferably each independently a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, 3-sulfopropoxy group, or 4-sulfobutoxy group, and particularly preferably a hydrogen atom , A methyl group, a methoxy group, or a 3-sulfopropoxy group.
- the positions on the phenyl group of Rr 1 to Rr 4 are preferably only the 2-position of the phenyl group, the 5-position only, the 2-position and 6-position combination, the 2-position and 5-position combination, and the 3-position and 5-position. Particularly preferred are the 2-position only, the 5-position only, and the 2-position and 5-position combination.
- “2-position only,” and a “5-position only” is, for Rr 1 and Rr 2, both Rr 1 and Rr 2 is situated at the 2-position or 5-position, with one substituent other than a hydrogen atom Yes, and the other means a hydrogen atom.
- Rr 3 and Rr 4 The same applies to Rr 3 and Rr 4 .
- the azo compound represented by the formula (1a) is preferably an azo compound represented by the formula (1a ′).
- the polarization performance of the polarizing element can be further improved.
- Ar 1 and Rr 1 to Rr 4 are as defined for formula (1a).
- Av 1 represents a phenyl group or a naphthyl group having at least one substituent selected from a sulfo group and a carboxy group.
- Av 1 is a phenyl group, it has at least one substituent selected from a sulfo group or a carboxy group.
- the phenyl group has two or more substituents, at least one of the substituents is a sulfo group or a carboxy group, and the other substituents are preferably a sulfo group, a carboxy group, a lower alkyl group, a lower alkoxy group.
- the lower alkoxy group having a sulfo group is preferably a straight-chain alkoxy like the above-mentioned 3-sulfopropoxy group or 4-sulfobutoxy group, and the substitution position of the sulfo group is preferably at the terminal of the alkoxy group. preferable.
- the number of sulfo groups is preferably one or two, and the substitution position of the sulfo group is not particularly limited.
- the number of carboxy groups is preferably 1 or 2, and the substitution position of the carboxy group is not particularly limited.
- the 4-position of the phenyl group is preferred, and in the case of two carboxy groups, the combination of the 2-position and 4-position or the combination of the 3-position and 5-position of the phenyl group is preferred.
- Av 1 is a naphthyl group, it preferably has at least one sulfo group as a substituent.
- the naphthyl group has two or more substituents, at least one of the substituents is a sulfo group, and the other substituents are a sulfo group, a hydroxy group, a carboxy group, and a lower alkoxy group having a sulfo group.
- the lower alkoxy group having a sulfo group is preferably linear alkoxy, and the substitution position of the sulfo group is preferably the terminal of the alkoxy group.
- Such a lower alkoxy group having a sulfo group is more preferably a 3-sulfopropoxy group or a 4-sulfobutoxy group, and particularly preferably a 3-sulfopropoxy group.
- the substitution position of the sulfo group is the 4-position, 8-position combination or 6-position of the naphthyl group, A combination at the 8th position is preferable, and a combination at the 6th and 8th positions is more preferable.
- the substitution position of the sulfo group is preferably a combination of the 3rd, 6th and 8th positions.
- the substitution position of the sulfo group is preferably a substitution position such as the 3-position, 4-position, 6-position or 8-position of the naphthyl group.
- the present invention is not limited to this.
- Rv 1 to Rv 6 each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy group having a sulfo group.
- the lower alkoxy group having a sulfo group straight-chain alkoxy is preferable, or the substitution position of the sulfo group is preferably the terminal of the alkoxy group.
- Rv 1 to Rv 6 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a 3-sulfopropoxy group, or a 4-sulfobutoxy group, and particularly preferably a hydrogen atom.
- Rv 6 is a hydrogen atom or a methyl group
- polarization performance of the polarizing element or polarizing plate is preferably used to further improve.
- Rv 5 and Rv 6 are a hydrogen atom and a methyl group
- the polarizing performance of the polarizing element or polarizing plate is significantly improved, which is preferable.
- Xv 1 has at least one substituent selected from the group consisting of a lower alkyl group, a lower alkoxy group, a sulfo group, an amino group, a lower alkylamino group, a hydroxy group, a carboxy group, and a carboxyethylamino group. And may represent an amino group, a phenylamino group, a phenylazo group, a naphthotriazole group or a benzoylamino group.
- Xv 1 is an amino group which may have a substituent
- the amino group is unsubstituted or, preferably, a lower alkyl group, a lower alkoxy group, a sulfo group, an amino group, and 1 or 2 substituents selected from the group consisting of lower alkylamino groups, more preferably selected from the group consisting of methyl groups, methoxy groups, sulfo groups, amino groups, and lower alkylamino groups It has one or two substituents.
- the amino group which may have a substituent excludes an amino group having a ring structure such as a phenylamino group.
- Xv 1 is an optionally substituted phenylamino group
- the phenylamino group is unsubstituted or preferably, a lower alkyl group, a lower alkoxy group, a sulfo group, an amino group
- one or two substituents selected from the group consisting of lower alkylamino groups, more preferably a substituent selected from the group consisting of methyl groups, methoxy groups, sulfo groups, and amino groups Have one or two.
- xv 1 is also good phenylazo group which may have a substituent
- the phenylazo group is unsubstituted or, preferably, hydroxy group, lower alkyl group, a lower alkoxy group, an amino group and, 1 to 3 substituents selected from the group consisting of carboxyethylamino groups, more preferably 1 to 3 substituents selected from the group consisting of methyl group, methoxy group, amino group, and hydroxy group Have one.
- xv 1 is a good naphthotriazole group which may have a substituent
- the naphthotriazole group is unsubstituted or, preferably from the group consisting of sulfo group, an amino group and carboxy group, It has one or two selected substituents, more preferably one or two sulfo groups as substituents.
- Xv 1 is an optionally substituted benzoylamino group
- the benzoylamino group is unsubstituted or preferably consists of a hydroxy group, an amino group, and a carboxyethylamino group It has one substituent selected from the group, and more preferably has one or two hydroxy groups or amino groups as substituents.
- Xv 1 is preferably a benzoylamino group which may have a substituent or a phenylamino group which may have a substituent, more preferably a phenylamino which may have a substituent. It is a group.
- the position of the substituent is not particularly limited, but when the phenylamino group has a substituent, one of the substituents is preferably p-position with respect to the amino group, and when the benzoylamino group has a substituent, One of the groups is preferably p-position to the carbonyl group.
- the azo compound represented by the formula (1b) is particularly preferably an azo compound represented by the formula (1b ′).
- the polarization performance of the polarizing element can be further improved.
- azo compounds represented by the formula (1a) or (1b) may be used alone or in combination of two or more. In one embodiment, both an azo compound represented by formula (1a) and an azo compound represented by formula (1b) may be used.
- the azo compound represented by the formula (1a) or a salt thereof can be synthesized by, for example, a method described in JP-A-2009-155364 and a similar method, but is not limited thereto. Absent.
- an azo compound represented by the formula (1a) is prepared by reacting a base compound represented by the formula (v) described later with a ureating agent such as phenyl chlorocarbonate at 20 to 95 ° C. be able to.
- a ureido synthesis method a method of ureido an amine compound using a phosgene compound or the like is known. By this synthesis method, an azo compound represented by the formula (1a) having a ureido skeleton can be obtained.
- a specific method for synthesizing the azo compound represented by the formula (1a) will be described below.
- amines having a substituent represented by the formula (i) are described in, for example, Yutaka Hosoda, “Dye Chemistry”, Gihodo, 1957, p.
- a diazotization is carried out by a production method similar to the production method described in 135-234, followed by coupling with an aniline represented by formula (ii) to obtain a monoazoamino compound represented by formula (iii).
- Ar represents the same as Ar 1 in formula (1a).
- R 1 and R 2 are the same as Rr 1 and Rr 2 in formula (1a), respectively).
- Ar represents the same as Ar 1 in formula (1a), and R 1 and R 2 represent the same as Rr 1 and Rr 2 in formula (1a), respectively).
- the monoazoamino compound represented by the formula (iii) is diazotized and further subjected to secondary coupling with the aniline represented by the formula (iv) to obtain the disazoamino compound represented by the formula (v).
- R 3 and R 4 are the same as Rr 3 and Rr 4 in formula (1a), respectively
- Ar represents the same as Ar 1 in formula (1a)
- R 1 and R 2 represent the same as Rr 1 and Rr 2 in formula (1a), respectively
- R 3 and R 4 represent formula ( And represents the same as Rr 3 and Rr 4 in 1a).
- the diazotization step in the above reaction route is performed by a conventional method such as mixing a nitrite such as sodium nitrite into a mineral acid aqueous solution or suspension of diazo component such as hydrochloric acid or sulfuric acid, or neutral or diazo component. Nitrite is added to a weak alkaline aqueous solution, and this is mixed with a mineral acid.
- the diazotization temperature is suitably -10 to 40 ° C.
- the coupling step with anilines is carried out by mixing an acidic aqueous solution such as hydrochloric acid or acetic acid with each of the above diazo liquids and at a temperature of ⁇ 10 to 40 ° C. under acidic conditions of pH 2 to 7.
- the monoazoamino compound or disazoamino compound obtained by the coupling step can be taken out as it is or precipitated by aciding out or salting out and filtered, or can be further processed as a solution or suspension.
- the diazonium salt is sparingly soluble and is a suspension
- the suspension can be filtered and the filtered diazonium salt can be used as a press cake in a further coupling step.
- the azo compound represented by the formula (1a) is synthesized by subjecting the disazoamino compound obtained in the above step to ureido reaction with phenyl chlorocarbonate.
- the ureido reaction is carried out under neutral to alkaline conditions at a temperature of 10 to 90 ° C. and a pH of 7 to 11, for example, by the production method described in JP-A-2009-155364.
- the azo compound obtained by salting out is precipitated and then filtered. If purification is required, salting out may be repeated or an azo compound obtained from water may be precipitated using an organic solvent.
- the organic solvent used for purification include water-soluble organic solvents such as alcohols such as methanol and ethanol, and ketones such as acetone.
- the azo compound represented by the formula (1a) can be synthesized.
- the azo compound represented by the formula (1b) can be produced by, for example, the methods described in WO2012 / 108169 and WO2012 / 108173, but is not limited thereto.
- Ag 1 represents a phenyl group having a substituent or a naphthyl group having a substituent.
- Ag 1 is a phenyl group, it preferably has at least one substituent selected from a sulfo group and a carboxy group.
- the phenyl group has two or more substituents, at least one of the substituents is a sulfo group or a carboxy group, and the other substituents are a sulfo group, a carboxy group, a lower alkyl group, a lower alkoxy group, a sulfo group.
- the other substituent is more preferably a sulfo group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a carboxy group, a nitro group, or an amino group, and particularly preferably a sulfo group, a methyl group, a methoxy group, or an ethoxy group. Group or carboxy group.
- the lower alkoxy group having a sulfo group is preferably linear alkoxy, and the substitution position of the sulfo group is preferably the end of the alkoxy group, more preferably a 3-sulfopropoxy group and a 4-sulfobutoxy group, particularly preferably 3- It is a sulfopropoxy group.
- the number of substituents possessed by the phenyl group is preferably 1 or 2, and the substitution position is not particularly limited. However, when the position of the azo group is the 1st position, only the 4th position is combined with the 2nd and 4th positions, and The 5-position combination is preferred.
- Ag 1 is a naphthyl group having a substituent
- the naphthyl group has two or more substituents, at least one of the substituents is a sulfo group, and the other substituents are a sulfo group, a hydroxy group, a carboxy group, or a lower alkoxy group having a sulfo group. It is preferable.
- the naphthyl group particularly preferably has two or more sulfo groups as substituents.
- the lower alkoxy group having a sulfo group is preferably straight-chain alkoxy, and the substitution position of the sulfo group is preferably the end of the alkoxy group, more preferably a 3-sulfopropoxy group and a 4-sulfobutoxy group, particularly preferably 3 A sulfopropoxy group.
- the substitution position of the sulfo group is preferably a combination of the 4th and 8th positions, and a combination of the 6th and 8th positions, with the position of the azo group being the 2nd position.
- the combination of the position and the eighth position is more preferable.
- the substitution position of the sulfo group is preferably a combination of the 3rd, 6th and 8th positions.
- Bg and Cg are each independently represented by the formula (BC-N) or (BC-P), and at least one of Bg and Cg is represented by the formula (BC-N).
- Cg is preferably represented by the formula (BC-N).
- Rg 1 each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy group having a sulfo group.
- Rg 1 is a hydrogen atom, a lower alkyl group, or a lower alkoxy group, more preferably a hydrogen atom, a methyl group, or a methoxy group.
- Particularly preferred Rg 1 is a hydrogen atom or a methoxy group.
- the lower alkoxy group having a sulfo group is preferably linear alkoxy, and the substitution position of the sulfo group is preferably the end of the alkoxy group, more preferably a 3-sulfopropoxy group and a 4-sulfobutoxy group, particularly preferably 3- It is a sulfopropoxy group.
- the substitution position of Rg 1 is preferably the 2-position or the 3-position with respect to the azo group substituted with Ag 1 , and more preferably the 3-position when the azo group on the Ag 1 side is the 1-position.
- the substitution position of the sulfo group is preferably 6-position or 7-position, more preferably 6-position.
- k represents an integer of 0 to 2.
- Rg 2 and Rg 3 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy group having a sulfo group, preferably a hydrogen atom, a methyl group, a methoxy group Group, 3-sulfopropoxy group, or 4-sulfopropoxy group.
- Xg 1 represents an amino group that may have a substituent, a phenylamino group that may have a substituent, a phenylazo group that may have a substituent, or a benzoylamino group that may have a substituent. Indicates.
- Xg 1 is preferably an amino group that may have a substituent or a phenylamino group that may have a substituent, and more preferably a phenylamino group that may have a substituent.
- “may have a substituent” means that a case where no substituent is present is included.
- an optionally substituted phenyl group includes an unsubstituted mere phenyl group and a phenyl group having a substituent.
- the amino group which may have a substituent is preferably an amino group having one or two selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, a sulfo group, an amino group, and a lower alkylamino group. More preferably an amino group having one or two selected from the group consisting of a hydrogen atom, a methyl group, and a sulfo group.
- An amino group having a ring structure such as a phenylamino group is excluded from an amino group which may have a substituent.
- the phenylamino group which may have a substituent is preferably one or two selected from the group consisting of a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, an amino group, and a lower alkylamino group.
- a phenylamino group having a substituent more preferably a phenylamino group having one or two substituents selected from the group consisting of a hydrogen atom, a methyl group, a methoxy group, a sulfo group, and an amino group; .
- the substitution position is not particularly limited, but one of the substituents is particularly preferably p-position with respect to the amino group of the phenylamino group.
- the phenylazo group which may have a substituent is preferably a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group, a hydroxy group, and a carboxyethylamino group.
- the benzoylamino group which may have a substituent is preferably a benzoylamino group having one substituent selected from the group consisting of a hydrogen atom, a hydroxy group, an amino group, and a carboxyethylamino group.
- the azo compound represented by the formula (2) or a salt thereof is preferably the azo compound represented by the formula (2 ′) or a salt thereof because performance is particularly improved.
- Ag 1 is as defined for Ag 1 in equation (2).
- Rg 4 and Rg 5 are each independently as defined for Rg 1 in formula (BC-N).
- Xg 1 is as defined for Xg 1 in formula (2).
- k 1 and k 2 each independently represents an integer of 0 to 2.
- the content of the azo compound represented by the formula (2) or a salt thereof is 0.01 to 100 parts by mass with respect to 100 parts by mass of the azo compound of the formula (1a) or (1b).
- the amount is preferably 5000 parts by mass, more preferably 0.1 to 3000 parts by mass.
- Examples of the azo compound represented by the formula (2) or a salt thereof include, for example, JP-A-01-161202, JP-A-01-172907, JP-A-01-248105, JP-A-01-265205, and JP-A-01-265205. Although it can be synthesized by the method described in Japanese Patent Application Publication No. 01-172907, etc., it is not limited thereto.
- azo compound represented by the formula (2) include, for example, C. I. Direct Blue 34, C. I. Direct Blue 69, C. I. Direct Blue 70, C. I. Direct Blue 71, C. I. Direct Blue 72, C. I. Direct Blue 75, C. I. Direct Blue 78, C. I. Direct Blue 81, C. I. Direct Blue 82, C. I. Direct Blue 83, C. I. Direct Blue 186, C. I. Direct Blue 258, Benzo Fast Chrome Blue FG (C.I. 34225), Benzo Fast Blue BN (C.I. 34120), C. I. Direct Green 51, An azo compound such as
- a polarizing element is higher than the conventional polarizing plate by containing the combination of the azo compound or its salt represented by Formula (1a) or (1b), and the azo compound or its salt represented by Formula (2). While having a transmittance and a high degree of polarization, it is possible to realize white, commonly known as paper white, such as high-quality paper during white display.
- the azo compound represented by formula (1a) or (1b) or a salt thereof and the azo compound represented by formula (2) or a salt thereof in addition to the azo compound represented by formula (1a) or (1b) or a salt thereof and the azo compound represented by formula (2) or a salt thereof, It is preferable that at least one of the azo compounds represented by (3) or a salt thereof is further contained.
- Ay 1 represents a sulfo group, a carboxy group, a hydroxy group, a lower alkyl group, or a lower alkoxy group, preferably a sulfo group, a carboxy group, or a lower alkoxy group, more preferably A sulfo group, a carboxy group, a methoxy group, or an ethoxy group, more preferably a sulfo group or a carboxy group.
- Ry 1 to Ry 4 each independently represents a hydrogen atom, a sulfo group, a lower alkyl group, or a lower alkoxy group having a lower alkoxy group or a sulfo group, preferably a hydrogen atom, a sulfo group, a methyl group, or an ethyl group , A methoxy group, or an ethoxy group, and more preferably a hydrogen atom, a sulfo group, a methyl group, or a methoxy group.
- P is an integer from 1 to 3.
- the azo compound represented by the formula (3) affects the transmittance of 400 to 500 nm.
- the transmittance and the degree of polarization (dichroism) on the short wavelength side of 400 to 500 nm affect the omission of blue when displaying black and the whiteness of yellow when displaying white.
- the azo compound represented by the formula (3) does not reduce the transmittance on the short wavelength side of the parallel position of the polarizing element, improves the polarization characteristics (dichroism) at 400 to 500 nm, and displays white. It is possible to further reduce the omission of blue when displaying the yellowish color and black color.
- the polarizing element according to the present invention can provide a polarizing element that exhibits a more neutral hue and has a higher degree of polarization.
- the azo compound represented by the formula (3) or a salt thereof can be synthesized by, for example, a method described in WO2007 / 138980 or the like, and a commercially available product can also be used.
- Examples of the azo compound represented by the formula (3) include C.I. I. Direct Yellow 4, C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 72, C.I. I. Examples include Direct Orange 39 and azo compounds having a stilbene structure described in WO2007 / 138980 and the like, but are not limited thereto.
- the azo compound represented by the formula (3) may be used alone or in combination of two or more.
- the polarizing element of the present invention has the formula (1a) for improving the polarization performance. It is preferable to contain both the azo compound represented by these, or its salt, and the azo compound represented by Formula (1b), or its salt.
- the polarizing element is a combination of an azo compound represented by formula (1a), an azo compound represented by formula (1b), an azo compound represented by formula (2), and an azo compound represented by formula (3).
- an azo compound represented by formula (1a) is a combination of an azo compound represented by formula (1a), an azo compound represented by formula (1b), an azo compound represented by formula (2), and an azo compound represented by formula (3).
- the azo compound represented by formula (1a), the azo compound represented by formula (1b), the azo compound represented by formula (2), and the azo compound represented by formula (3) were in free form.
- it may be in the form of a salt.
- the salt can be, for example, an alkali metal salt such as a lithium salt, a sodium salt, and a potassium salt, or an organic salt such as an ammonium salt or an alkylamine salt.
- the salt is preferably a sodium salt.
- the polarizing element according to the present invention contains an azo compound represented by formula (1a) or (1b) and an azo compound represented by formula (2), and an azo compound optionally represented by formula (1a) It contains both of the azo compounds represented by formula (1b), and optionally further contains an azo compound represented by formula (3).
- the polarizing element according to the present invention can have performances such as desired chromaticity a * and b * values, single transmittance, and average transmittance in a specific wavelength band, which will be described later.
- the blending ratio of the azo compound in the polarizing element is further adjusted so that the transmittance and chromaticity are within the preferable ranges described later in the content of each azo compound described above.
- the performance of the polarizing element is not only the compounding ratio of each azo compound in the polarizing element, but also various factors such as the degree of swelling and stretching ratio of the substrate that adsorbs the azo compound, dyeing time, dyeing temperature, pH during dyeing, and the influence of salt. It depends on various factors. For this reason, the compounding ratio of each azo compound can be determined according to the swelling degree of the substrate, the temperature at the time of dyeing, the time, the pH, the type of salt, the concentration of the salt, and further the draw ratio. Such a mixing ratio can be determined by those skilled in the art without trial and error based on the following description.
- the transmittance is the transmittance after the visibility correction, which is obtained according to JIS Z 8722: 2009.
- the transmittance is measured by measuring the spectral transmittance every 5 nm or 10 nm for each wavelength of 400 to 700 nm for a measurement sample (for example, a polarizing element or a polarizing plate), and measuring this twice with a visual field (C light source). It can be obtained by correcting the visibility.
- the difference in average transmittance between specific wavelength bands is preferably not more than a predetermined value.
- the average transmittance is an average value of transmittance in a specific wavelength band.
- the wavelength bands of 420 nm to 480 nm, 520 nm to 590 nm, and 600 nm to 640 nm are the main wavelength bands based on the color matching function used in the calculation when showing colors in JIS Z 8781-4: 2013.
- each wavelength indicating a value of 20 or more is a wavelength band of 420 nm to 480 nm, 520 nm to 590 nm, and 600 nm to 640 nm.
- the polarizing element of the present invention has a transmittance (hereinafter referred to as “parallel”) obtained by measuring a state in which two polarizing elements are arranged so as to be parallel in the absorption axis direction (at the time of bright display or at the time of white display).
- the absolute value of the difference between the average transmittance from 420 nm to 480 nm and the average transmittance from 520 nm to 590 nm is preferably 2.5% or less, more preferably 1.8%. % Or less, more preferably 1.5% or less, and particularly preferably 1.0% or less.
- the absolute value of the difference between the average transmittance from 520 nm to 590 nm and the average transmittance from 600 nm to 640 nm is preferably 2.0% or less, more preferably 1.5% or less. More preferably, it is 1.0% or less.
- Such a polarizing element can display a white color like a high-quality paper in a parallel position.
- the transmittance (hereinafter referred to as “orthogonal transmission”) obtained by measuring the state in which two polarizing elements are stacked so that the absorption axis directions are orthogonal to each other (during black display or dark display).
- the absolute value of the difference between the average transmittance from 420 nm to 480 nm and the average transmittance from 520 nm to 590 nm is 10% or less, and the average transmittance from 520 nm to 590 nm and from 600 nm to 640 nm.
- the absolute value of the difference from the average transmittance is preferably 2.0% or less, and more preferably 1% or less.
- Such a polarizing element can display achromatic black at an orthogonal position.
- the absolute value of the difference between the average transmittance from 420 nm to 480 nm and the average transmittance from 520 nm to 590 nm is preferably 2% or less, more preferably 1% or less.
- the absolute value of the difference between the average transmittance from 520 nm to 590 nm and the average transmittance from 600 nm to 640 nm is preferably 0.5% or less, more preferably 0.2% or less, and still more preferably 0.1% or less.
- the average transmittance of the single transmittance, parallel transmittance, and orthogonal transmittance in each of the wavelength bands 380 nm to 420 nm, 480 nm to 520 nm, and 640 nm to 780 nm is from the wavelength bands 420 nm to 480 nm and 520 nm.
- the average transmittance at 590 nm and 600 nm to 640 nm is adjusted as described above, it is difficult to be greatly affected by the dye, but it is preferably adjusted to some extent.
- the difference between the average transmittance of the wavelength band 380 nm to 420 nm and the average transmittance of 420 nm to 480 nm is preferably 15% or less, and the difference between the average transmittance of 480 nm to 520 nm and the average transmittance of 420 nm to 480 nm 15% or less.
- the difference between the average transmittance from 480 nm to 520 nm and the average transmittance from 520 nm to 590 nm is 15% or less
- the difference between the average transmittance from 640 nm to 780 nm and the average transmittance from 600 nm to 640 nm is 20% The following is preferable.
- the polarizing element according to the present invention preferably has a single transmittance of 35% to 65%.
- the single transmittance is a transmittance obtained by correcting the visibility of one measurement sample (for example, a polarizing element or a polarizing plate) according to JIS Z 8722: 2009.
- the performance of the polarizing plate is required to be higher, but if the single transmittance is 35% to 60%, even if it is used for a display device, brightness can be expressed without a sense of incongruity.
- the single transmittance is more preferably 37% to 50%, and even more preferably 38% to 45%. is there. If the single transmittance exceeds 65%, the degree of polarization may decrease. However, when obtaining a bright transmittance of a polarizing element or specific polarization performance or contrast, the single transmittance may exceed 65%. Good.
- the polarizing element preferably has an average transmittance of 28% to 50% in the wavelength band of 520 nm to 590 nm measured in parallel.
- Such a polarizing element can be a bright and clear display device when provided in the display device.
- the transmittance in the wavelength band from 520 nm to 590 nm is one of the main wavelength bands based on the color matching function used in the calculation when the color is shown in JIS Z 8781-4: 2013.
- each wavelength band from 520 nm to 590 nm is the wavelength band with the highest visibility based on the color matching function, and the transmittance in this range is close to the transmittance that can be visually confirmed.
- the average transmittance of the wavelength band of 520 nm to 590 nm measured in parallel is more preferably 29% to 45%, and further preferably 30% to 40%.
- the degree of polarization of the polarizing element at this time is preferably 80% to 100%, more preferably 95% to 100%, and still more preferably 99% to 100%.
- the degree of polarization is preferably high, but in the relationship between the degree of polarization and the transmittance, the transmittance and the degree of polarization should be adjusted to be suitable depending on whether the importance is on brightness or the degree of polarization (or contrast). Can do.
- the chromaticity a * value and b * value are values obtained when measuring the transmittance of natural light according to JIS Z 8781-4: 2013.
- the object color display method defined in JIS Z 8781-4: 2013 corresponds to the object color display method defined by the International Commission on Illumination (abbreviation: CIE).
- the chromaticity a * value and b * value are measured by irradiating a measurement sample (for example, a polarizing element or a polarizing plate) with natural light.
- the chromaticity a * value and b * value obtained for one measurement sample are a * -s and b * -s, and two measurement samples are arranged so that their absorption axis directions are parallel to each other.
- the chromaticity a * and b * values required for the state (when white is displayed) are a * -p and b * -p, and two measurement samples are arranged so that their absorption axis directions are perpendicular to each other (black display)
- the chromaticity a * value and b * value obtained for (time) are denoted as a * -c and b * -c.
- each of the absolute values of a * -s and b * -s is preferably 5.0 or less, and more preferably 1.0 or less.
- Each of the absolute values of a * -p and b * -p is preferably 2.0 or less.
- Such a polarizing element is a neutral color by itself, and can display a high-quality white when displaying white.
- the absolute values of a * -p and b * -p of the polarizing element are more preferably 1.5 or less, and even more preferably 1.0 or less.
- each of the absolute values of a * -c and b * -c is preferably 20.0 or less, more preferably 10.0 or less, and even more preferably 3.0 or less. Particularly preferably, it is 1.0 or less.
- Such a polarizing element can display achromatic black when displaying black. Even if there is only a difference of 0.5 in the absolute value of the chromaticity a * value and b * value, a human can perceive the difference in color, and some people may feel the difference in color greatly. For this reason, it is very important to control these values in the polarizing element.
- the polarizing element according to the present invention has achromaticity and high polarization degree as a single unit while having high contrast and high transmittance. Further, the polarizing element of the present invention can express white (paper white) such as high-quality paper at the time of white display, and further, the polarizing element of the present invention has a high contrast, so that the achromatic color at the time of black display It is possible to express clear black, particularly high-quality and clear black. Until now, there has been no polarizing element having such a high transmittance and achromatic property. The polarizing element of the present invention is further highly durable, and particularly has durability against high temperatures and high humidity.
- the polarizing element according to the present invention has less absorption of light having a wavelength of 700 nm or more than that of a commonly used iodine-based polarizing plate or Patent Document 3, and therefore generates heat even when irradiated with light such as sunlight.
- a polarizing element is also irradiated.
- Sunlight also includes light having a wavelength of 700 nm or more, and includes near infrared rays having a heat generation effect.
- 02-061988 absorbs near-infrared light having a wavelength of around 700 nm and generates a little heat. Since the polarizing element absorbs very little near infrared light, it generates little heat even when exposed to sunlight outdoors.
- the polarizing element of the present invention is excellent in that it is less deteriorated due to less heat generation.
- a specific method for producing a polarizing element will be described by taking as an example a case where an azo compound is adsorbed on a substrate made of polyvinyl alcohol resin.
- the manufacturing method of the polarizing element which concerns on this invention is not limited to the following manufacturing methods.
- the raw film can be produced by forming a polyvinyl alcohol-based resin.
- a polyvinyl alcohol-type resin is not specifically limited, A commercially available thing may be used and what was synthesize
- the polyvinyl alcohol resin can be obtained, for example, by saponifying a polyvinyl acetate resin.
- the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.
- the saponification degree of the polyvinyl alcohol-based resin is usually preferably about 85 to 100 mol%, more preferably 95 mol% or less.
- the polyvinyl alcohol resin may be further modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
- the degree of polymerization of the polyvinyl alcohol-based resin means a viscosity average degree of polymerization, and can be determined by a well-known technique in the technical field, and is usually preferably about 1,000 to 10,000, more preferably a degree of polymerization of 1, It is about 500 to 6,000.
- the method for forming the polyvinyl alcohol-based resin is not particularly limited, and can be formed by a known method.
- the polyvinyl alcohol-based resin film may contain glycerin, ethylene glycol, propylene glycol, low molecular weight polyethylene glycol, or the like as a plasticizer.
- the amount of the plasticizer is preferably 5 to 20% by mass, more preferably 8 to 15% by mass, based on the total amount of the film.
- the film thickness of the raw film is not particularly limited, but is, for example, about 5 ⁇ m to 150 ⁇ m, preferably about 10 ⁇ m to 100 ⁇ m.
- the raw film obtained as described above is subjected to swelling treatment.
- the swelling treatment is preferably performed by immersing the raw film in a solution at 20 to 50 ° C. for 30 seconds to 10 minutes.
- the solution is preferably water.
- the draw ratio is preferably adjusted to 1.00 to 1.50 times, more preferably 1.10 to 1.35 times.
- the swelling process can be omitted because the raw film swells also during the dyeing process described later.
- the dyeing step an azo compound is adsorbed and impregnated into a resin film obtained by swelling the raw film.
- the swelling process is omitted, the swelling process of the original film can be performed simultaneously in the dyeing process. Since the treatment of adsorbing and impregnating the azo compound is a step of coloring the resin film, it is a dyeing step.
- an azo compound represented by the formula (1a) or (1b) or a salt thereof and a mixture of the azo compound represented by the formula (2) or a salt thereof, and optionally the formula (3), or An azo compound represented by the formula (4) or a salt thereof can be further used.
- an azo compound which is a dichroic dye exemplified in “Application of Functional Dye” (CMC Publishing Co., Ltd., 1st printing edition, supervised by Masahiro Irie, pages 98 to 100), etc. You may adjust a color using it to such an extent that the performance of an element is not impaired.
- These azo compounds may be used in the form of a free acid or a salt of the compound.
- Such salts are, for example, alkali metal salts such as lithium salts, sodium salts, and potassium salts, or organic salts such as ammonium salts and alkylamine salts, and preferably sodium salts.
- the dyeing step is not particularly limited as long as it is a method for adsorbing and impregnating the dye to the resin film, but for example, it is preferably performed by immersing the resin film in the dyeing solution, and is performed by applying the dyeing solution to the resin film. You can also.
- Each azo compound in the dyeing solution can be adjusted, for example, within a range of 0.001 to 10% by mass.
- the solution temperature in this step is preferably 5 to 60 ° C., more preferably 20 to 50 ° C., and particularly preferably 35 to 50 ° C.
- the time for dipping in the solution can be adjusted moderately, but is preferably adjusted from 30 seconds to 20 minutes, more preferably from 1 to 10 minutes.
- the dyeing solution may further contain a dyeing assistant as required in addition to the azo compound.
- the dyeing assistant include sodium carbonate, sodium hydrogen carbonate, sodium chloride, sodium sulfate, anhydrous sodium sulfate, and sodium tripolyphosphate.
- the content of the dyeing assistant can be adjusted at an arbitrary concentration depending on the time and temperature depending on the dyeability of the dye.
- the content of each dye is preferably 0.01 to 5% by mass in the dyeing solution, preferably 0.1 to 2 mass% is more preferable.
- the dyeing process 1 is a process of washing the dyeing solution adhering to the surface of the resin film in the dyeing process. By performing the washing step 1, it is possible to suppress the migration of the dye into the liquid to be processed next.
- water is generally used as the cleaning liquid.
- the washing method is preferably immersed in a washing solution, but can be washed by applying the washing solution to a resin film.
- the washing time is not particularly limited, but is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.
- the temperature of the cleaning liquid in the cleaning step 1 needs to be a temperature at which a material constituting the resin film (for example, a hydrophilic polymer, here, a polyvinyl alcohol-based resin) does not dissolve. Generally, it is washed at 5 to 40 ° C. However, even if there is no cleaning process 1, there is no problem in performance, so the cleaning process can be omitted.
- a material constituting the resin film for example, a hydrophilic polymer, here, a polyvinyl alcohol-based resin
- Step of containing a crosslinking agent and / or a water resistance agent After the dyeing step or the washing step 1, a step of adding a crosslinking agent and / or a water resistance agent can be performed.
- the method of adding a crosslinking agent and / or a water resistance agent to the resin film is preferably immersed in the treatment solution, but the treatment solution may be applied or applied to the resin film.
- the treatment solution contains at least one crosslinking agent and / or waterproofing agent and a solvent.
- the temperature of the treatment solution in this step is preferably 5 to 70 ° C, and more preferably 5 to 50 ° C.
- the treatment time in this step is preferably 30 seconds to 6 minutes, more preferably 1 to 5 minutes.
- crosslinking agent examples include boron compounds such as boric acid, borax or ammonium borate, polyvalent aldehydes such as glyoxal or glutaraldehyde, polyisocyanate compounds such as biuret type, isocyanurate type or block type, titanium oxy Titanium compounds such as sulfate can be used, but ethylene glycol glycidyl ether, polyamide epichlorohydrin, and the like can also be used.
- boron compounds such as boric acid, borax or ammonium borate
- polyvalent aldehydes such as glyoxal or glutaraldehyde
- polyisocyanate compounds such as biuret type, isocyanurate type or block type
- titanium oxy Titanium compounds such as sulfate can be used, but ethylene glycol glycidyl ether, polyamide epichlorohydrin, and the like can also be used.
- water-resistant agents include succinic peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride or magnesium chloride, preferably boric acid.
- the solvent for the cross-linking agent and / or water-resistant agent is preferably, but not limited to, water.
- the concentration of the crosslinking agent and / or water-resistant agent can be appropriately determined by those skilled in the art depending on the type of the crosslinking agent. However, when boric acid is used as an example, the concentration in the treatment solution is 0.1 to 6.0 mass.
- % Is preferable and 1.0 to 4.0% by mass is more preferable.
- this processing step may be omitted if a cross-linking treatment or a water-resistant treatment is unnecessary. .
- the stretching process is performed by stretching the resin film uniaxially.
- the stretching method may be either a wet stretching method or a dry stretching method.
- the draw ratio is preferably 3 times or more, more preferably 4 to 8 times, and particularly preferably 5 to 7 times.
- the stretching heating medium is an air medium
- the humidity is preferably in an atmosphere of 20 to 95% RH.
- the heating method include an inter-roll zone stretching method, a roll heating stretching method, a pressure stretching method, and an infrared heating stretching method, but the stretching method is not limited.
- the stretching step can be performed in one stage, but can also be performed by multi-stage stretching of two or more stages.
- the resin film in water, a water-soluble organic solvent, or a mixed solution thereof. It is preferable to perform the stretching treatment while immersing in a solution containing at least one crosslinking agent and / or waterproofing agent.
- a crosslinking agent and a water-proofing agent the same thing as having mentioned above about the process of containing a crosslinking agent and / or a water-proofing agent can be used.
- the concentration of the crosslinking agent and / or waterproofing agent in the solution in the stretching step is, for example, preferably from 0.5 to 15% by mass, and more preferably from 2.0 to 8.0% by mass.
- the stretching temperature is preferably 40 to 70 ° C, more preferably 45 to 60 ° C.
- the stretching time is usually from 30 seconds to 20 minutes, more preferably from 2 to 5 minutes.
- the wet stretching step can be performed in one step, but can also be performed by two or more steps.
- cleaning process 2 After performing the stretching process, the cross-linking agent and / or waterproofing agent may precipitate on the resin film surface, or foreign matter may adhere to the resin film surface. Therefore, the cleaning process for cleaning the resin film surface (hereinafter referred to as “cleaning process 2”). Can be performed).
- the washing time is preferably 1 second to 5 minutes.
- As the cleaning liquid water is preferable.
- the cleaning process can be performed in one stage, and the multi-stage process of two or more stages can be performed.
- the solution temperature in the washing step is not particularly limited, but is usually 5 to 50 ° C., preferably 10 to 40 ° C.
- Examples of the treatment solution or solvent used in the treatment steps so far include water, for example, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, and triethylene.
- Examples include alcohols such as glycol, tetraethylene glycol or trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine, but are not limited thereto.
- the treatment liquid or its solvent is most preferably water. In addition, these treatment liquids or their solvents can be used alone or in a mixture of two or more.
- a resin film drying process is performed.
- the drying treatment can be performed by natural drying, but in order to further increase the drying efficiency, it can be performed by compressing with a roll, removing moisture on the surface with an air knife, a water absorbing roll, etc., and / or by air drying. It can also be done.
- the drying treatment temperature is preferably 20 to 100 ° C., more preferably 60 to 100 ° C.
- the drying treatment time is, for example, 30 seconds to 20 minutes, but preferably 5 to 10 minutes.
- the absolute value of the difference between the average transmittance from 420 nm to 480 nm and the average transmittance from 520 nm to 590 nm is 2.5 or less, and the average transmittance from 520 nm to 590 nm and from 600 nm to 640 nm
- the absolute value of the difference from the average transmittance is 2.0 or less.
- the absolute value of the difference between the average transmittance from 420 nm to 480 nm and the average transmittance from 520 nm to 590 nm is 10 or less, and the average transmittance from 520 nm to 590 nm and the average transmittance from 600 nm to 640 nm.
- the absolute value of the difference between and is 2.0 or less.
- the single transmittance is from 35% to 65%.
- the absolute values of the a * value and the b * value are both 1.0 or less for the polarizing element alone and 2.0 or less for the parallel position.
- a polarizing element containing at least a combination of the azo compound represented by formula (1a) or (1b) and the azo compound represented by formula (2) can be produced.
- Such a polarizing element has a higher transmittance and a higher degree of polarization than a conventional polarizing element, but it is like a high-quality paper when two polarizing elements are stacked so that the absorption axis directions are parallel to each other.
- a polarizing element that can express white color, has a neutral color (neutral gray) alone, and has high contrast can be manufactured. Further, the polarizing element has high durability against high temperatures and high humidity.
- the polarizing plate which concerns on this invention is equipped with a polarizing element and the transparent protective layer provided in the single side
- the transparent protective layer is provided for the purpose of improving the water resistance and handling properties of the polarizing element.
- the transparent protective layer is a protective film formed using a transparent substance.
- the protective film is a film having a layer shape capable of maintaining the shape of the polarizing element, and is preferably a plastic having excellent transparency, mechanical strength, thermal stability, moisture shielding properties, and the like.
- An equivalent function may be provided by forming an equivalent layer.
- plastics constituting the protective film include polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins and acrylic resins, Examples include films obtained from thermosetting resins such as acrylic, urethane, acrylic urethane, epoxy and silicone, or ultraviolet curable resins.
- polyolefin resins include amorphous polyolefin resins.
- a resin having a polymerized unit of cyclic polyolefin such as a norbornene-based monomer or a polycyclic norbornene-based monomer.
- a protective film that does not impair the performance of the polarizing element after laminating the protective film, and as such a protective film, triacetyl cellulose (TAC) and norbornene made of cellulose acetate resin are particularly preferable.
- the protective film may be subjected to a treatment for the purpose of hard coat treatment, antireflection treatment, prevention of sticking, diffusion, anti-glare, etc., as long as the effects of the present invention are not impaired.
- the polarizing plate preferably further includes an adhesive layer for bonding the transparent protective layer and the polarizing element between the transparent protective layer and the polarizing element.
- an adhesive agent which comprises an adhesive bond layer A polyvinyl alcohol-type adhesive agent is preferable.
- the polyvinyl alcohol-based adhesive include, but are not limited to, GOHSENOL NH-26 (manufactured by Nihon Gosei Co., Ltd.) and EXEVAL RS-2117 (manufactured by Kuraray Co., Ltd.).
- a cross-linking agent and / or a waterproofing agent can be added to the adhesive.
- a maleic anhydride-isobutylene copolymer is preferably used, and an adhesive mixed with a crosslinking agent can be used as necessary.
- the maleic anhydride-isobutylene copolymer include isoban # 18 (manufactured by Kuraray), isoban # 04 (manufactured by Kuraray), ammonia-modified isoban # 104 (manufactured by Kuraray), and ammonia-modified isoban # 110 (Kuraray).
- a water-soluble polyvalent epoxy compound can be used as the crosslinking agent at that time.
- the water-soluble polyvalent epoxy compound include Denacol EX-521 (manufactured by Nagase Chemtech) and Tetrat-C (manufactured by Mitsui Gas Chemical Co., Ltd.).
- adhesives other than polyvinyl alcohol-type resin well-known adhesives, such as urethane type, an acrylic type, and an epoxy type, can also be used.
- acetoacetyl-modified polyvinyl alcohol it is preferable to use acetoacetyl-modified polyvinyl alcohol, and it is preferable to use a polyvalent aldehyde as the cross-linking agent.
- additives such as zinc compounds, chlorides, and iodides may be contained alone or simultaneously at a concentration of about 0.1 to 10% by mass. You can also.
- the additive to an adhesive agent is not specifically limited, Those skilled in the art can select suitably.
- the polarizing plate when the polarizing plate is bonded to a display device such as a liquid crystal or organic electroluminescence (commonly referred to as OLED or OEL), the viewing angle and / or the contrast is improved on the surface of the protective layer or film that will be an unexposed surface later.
- a display device such as a liquid crystal or organic electroluminescence (commonly referred to as OLED or OEL)
- various functional layers and a layer or film having brightness enhancement can be provided.
- the various functional layers are, for example, layers or films that control the retardation.
- the polarizing plate is preferably bonded to these films and display devices with an adhesive.
- the polarizing plate may be provided with various well-known functional layers such as an antireflection layer, an antiglare layer, and a hard coat layer on the exposed surface of the protective layer or film.
- a coating method is preferable for producing the layer having various functions, but a film having the function can be bonded through an adhesive or a pressure-sensitive adhesive.
- the polarizing plate according to the present invention can achieve achromaticity while having a high transmittance and a high degree of polarization, and in particular, can express white such as high-quality paper when displaying white, It is a highly durable polarizing plate that can express contrast.
- the polarizing element or polarizing plate of the present invention is provided with a protective layer or functional layer and a transparent support such as glass, crystal, and sapphire as necessary, and includes a liquid crystal projector, a calculator, a clock, a notebook computer, a word processor, a liquid crystal television, It is applied to polarized lenses, polarized glasses, car navigation, indoor and outdoor measuring instruments and displays.
- the polarizing element or polarizing plate of the present invention is suitably used for liquid crystal display devices such as reflective liquid crystal display devices, transflective liquid crystal display devices, and organic electroluminescence.
- the liquid crystal display device using the polarizing element or polarizing plate of the present invention can express white and high contrast like high-quality paper.
- the liquid crystal display device is a liquid crystal display device having high durability, high reliability, long-term high contrast, and high color reproducibility.
- Example 1 A polyvinyl alcohol film (VF-PS manufactured by Kuraray Co., Ltd.) having a saponification degree of 99% or more and an average polymerization degree of 2400 was immersed in warm water at 45 ° C. for 2 minutes, and a swelling treatment was applied to make the draw ratio 1.30 times. 1500 parts by weight of water, 1.5 parts by weight of sodium tripolyphosphate, 1.5 parts by weight of anhydrous sodium sulfate, 0.32 parts by weight of Compound Example [1a-25] as a compound of formula (1a), and Compound Example [2 -4] in 45 ° C. dyeing solution containing 0.20 parts by mass of the film, the swollen film was immersed for 4 minutes and 30 seconds to contain the azo compound.
- VF-PS manufactured by Kuraray Co., Ltd.
- the obtained film was immersed in an aqueous solution at 40 ° C. containing 20 g / l of boric acid (manufactured by Societa Chimica Lardello sp.). The film after the immersion was stretched for 5 minutes in an aqueous solution at 50 ° C. containing 30.0 g / l of boric acid while being stretched 5.0 times. The obtained film was washed by immersing it in water at 25 ° C. for 20 seconds while maintaining its tension state. The washed film was dried at 70 ° C. for 9 minutes to obtain a polarizing element.
- boric acid manufactured by Societa Chimica Lardello sp.
- Example 2 instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ] As a compound of the formula (2), 0.32 parts by mass of C.I. I. A polarizing plate was produced in the same manner as in Example 1 except that 0.22 parts by mass of Direct Blue 69 was used.
- Example 3 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ] Is 0.32 parts by mass, Compound Example [2-4] is 0.20 parts by mass as a compound described in Formula (2), and Compound Example [3-1] is 0.27 parts by mass as a compound of Formula (3). A polarizing plate was produced in the same manner as in Example 1 except that the part was used.
- Example 4 A polarizing plate was produced in the same manner as in Example 3, except that the content of the azo compound was changed from 4 minutes 30 seconds to 3 minutes.
- Example 5 A polarizing plate was produced in the same manner as in Example 3 except that the content time of the azo compound was changed from 4 minutes 30 seconds to 2 minutes.
- Example 7 A polarizing plate was produced in the same manner as in Example 6 except that the content time of the azo compound was changed from 4 minutes 30 seconds to 3 minutes.
- Example 8 A polarizing plate was produced in the same manner as in Example 6 except that the content of the azo compound was changed from 4 minutes 30 seconds to 2 minutes.
- Example 9 A polarizing plate was produced in the same manner as in Example 6 except that the content of the azo compound was changed from 4 minutes 30 seconds to 1 minute.
- Example 10 instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ]
- a compound of the formula (2) 0.32 parts by mass of C.I. I.
- a polarizing plate was produced in the same manner as in Example 1 except that 0.22 parts by mass of Direct Blue 69 and 0.27 parts by mass of Compound Example [3-1] as a compound of the formula (3) were used.
- Example 11 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ]
- a polarizing plate was produced in the same manner as in Example 1 except that the part by mass was used.
- Example 12 instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ] Is 0.32 parts by mass, Compound Example [2-4] is 0.20 parts by mass as a compound described in Formula (2), C.I. I. A polarizing plate was produced in the same manner as in Example 1 except that 0.22 parts by mass of Direct Yellow 28 was used.
- Example 13 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-13 as a compound of formula (1a) ] Is 0.35 parts by mass, Compound Example [2-4] is 0.20 parts by mass as a compound described in Formula (2), and Compound Example [3-1] is 0.27 parts by mass as a compound of Formula (3). A polarizing plate was produced in the same manner as in Example 1 except that the part was used.
- Example 14 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1a-5 as a compound of formula (1a) ] Is 0.29 parts by mass, Compound Example [2-4] is 0.20 parts by mass as a compound described in Formula (2), and Compound Example [3-1] is 0.27 parts by mass as a compound of Formula (3). A polarizing plate was produced in the same manner as in Example 1 except that the part was used.
- Example 15 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ] Is 0.32 parts by mass, Compound Example [2-13] is 0.21 parts by mass as a compound described in Formula (2), and Compound Example [3-1] is 0.27 parts by mass as a compound of Formula (3). A polarizing plate was produced in the same manner as in Example 1 except that the part was used.
- Example 16 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ] Is 0.32 parts by mass, Compound Example [2-15] is 0.243 parts by mass as a compound described in Formula (2), and Compound Example [3-1] is 0.27 parts by mass as a compound of Formula (6). A polarizing plate was produced in the same manner as in Example 1 except that the part was used.
- Example 17 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1a-25 as a compound of formula (1a) ] 0.22 parts by mass of Compound Example [2-23] as a compound described in Formula (2) and 0.27 parts by mass of Compound Example [3-1] as a compound of Formula (3) A polarizing plate was produced in the same manner as in Example 1 except that the part was used.
- Example 18 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, and Compound Example [1b-33 as a compound of formula (1b) ] 0.15 parts by mass, 0.10 parts by mass of compound example [2-4] as a compound of formula (2), 0.05 parts by mass of compound example [3-1] as a compound of formula (3) A polarizing plate was produced in the same manner as in Example 1 except that the point used and the content of the azo compound were changed from 4 minutes 30 seconds to 8 minutes 00 seconds.
- Example 19 A polarizing plate was produced in the same manner as in Example 18 except that the time for containing the azo compound in the dyeing step for the swollen film was changed from 8 minutes to 4 minutes.
- Example 21 instead of the staining solution used in Example 19, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1b-33 as a compound of formula (1b) ] Of 0.15 parts by mass, compound example [2-4] as a compound of formula (2), 0.10 parts by mass, C.I. I. A polarizing plate was produced in the same manner as in Example 18 except that 0.05 part by mass of Direct Yellow 28 was used.
- Example 24 instead of the staining solution used in Example 19, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1b-35 as a compound of formula (1b) ] Is 0.22 parts by mass, Compound Example [2-17] is 0.10 parts by mass as a compound of Formula (2), and Compound Example [3-1] is 0.05 parts by mass as a compound of Formula (3).
- a polarizing plate was produced in the same manner as in Example 18 except that it was used.
- Example 25 instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1a] as a compound described in formula (1a) -25] is 0.20 parts by mass, Compound Example [1b-33] is 0.15 parts by mass as a compound described in Formula (1b), and Compound Example [2-17] is selected as a compound described in Formula (2) A polarizing plate was produced in the same manner as in Example 1, except that 0.1 part by mass and 0.05 part by mass of Compound Example [3-1] as the compound of the formula (3) were used.
- Example 26 A polarizing plate was produced in the same manner as in Example 25 except that the content time of the azo compound was changed from 4 minutes 30 seconds to 3 minutes.
- Example 27 instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1a] as a compound described in formula (1a) ⁇ 25] is 0.20 part by mass, Compound Example [1b-44] is 0.17 part by mass as a compound described in Formula (1b), and Compound Example [2-4] is as a compound described in Formula (2).
- a polarizing plate was produced in the same manner as in Example 1, except that 0.17 parts by mass and 0.05 part by mass of Compound Example [3-1] as the compound of the formula (3) were used.
- Example 28 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1a] as a compound described in formula (1a) -25] is 0.20 parts by mass, Compound Example [1b-56] is 0.23 parts by mass as a compound described in Formula (1b), and Compound Example [2-4] is specified as a compound described in Formula (2).
- a polarizing plate was produced in the same manner as in Example 1, except that 0.17 parts by mass and 0.05 part by mass of Compound Example [3-1] as the compound of the formula (3) were used.
- Example 29 Instead of the staining solution used in Example 1, 1500 parts by mass of water, 1.5 parts by mass of sodium tripolyphosphate, 1.5 parts by mass of anhydrous sodium sulfate, compound example [1a] as a compound described in formula (1a) Compound [1b-35] as 0.13 parts by mass of the compound described in Formula (1b) and 0.15 parts by mass of Compound [2-4] as the compound described in Formula (2) A polarizing plate was produced in the same manner as in Example 1, except that 0.17 parts by mass and 0.05 part by mass of Compound Example [3-1] as the compound of the formula (3) were used.
- Example 1 an aqueous solution (dye solution) containing an azo compound has the same composition as Example 1 of Patent Document 3, and the time for containing the azo compound (immersion time of the swollen PVA film in the dyeing tank) is a comparative example. 1 in the same manner as in Example 1 except that it was changed to 12 minutes in Comparative Example 2, 10 minutes in Comparative Example 2, 8 minutes in Comparative Example 3, 5 minutes and 30 seconds in Comparative Example 4, and 4 minutes in Comparative Example 5. Was added to prepare a polarizing plate.
- Comparative Examples 8 to 13 According to the production method of Comparative Example 1 of JP-A-2008-065222, the iodine content time was 5 minutes 30 seconds in Comparative Example 8, 4 minutes 45 seconds in Comparative Example 9, 4 minutes 15 seconds in Comparative Example 10, and Comparative Example No. 11 for 3 minutes 30 seconds, Comparative Example 12 for 4 minutes 00 seconds, and Comparative Example 13 for 5 minutes 15 seconds, an iodine-based polarizing plate containing no azo compound was prepared and used as a measurement sample.
- Example 15 A polarizing plate was prepared as in Example 1 of JP-A-11-218611 regarding a dye-based polarizing plate.
- a polarizing plate was produced as in Example 3 of JP-A-2001-033627 relating to a dye-based polarizing plate.
- a polarizing plate was prepared as in Example 1 of JP-A-2004-251962 relating to a dye-based polarizing plate.
- the measurement samples obtained in Examples 1 to 29 and Comparative Examples 1 to 18 were evaluated as follows.
- the single transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc of each measurement sample were measured using a spectrophotometer (“U-4100” manufactured by Hitachi, Ltd.).
- the single transmittance Ts is a transmittance of each wavelength when a single measurement sample is measured.
- the parallel transmittance Tp is a spectral transmittance of each wavelength measured by superimposing two measurement samples so that their absorption axis directions are parallel to each other.
- the orthogonal transmittance Tc is a spectral transmittance measured by overlapping two polarizing plates so that their absorption axes are orthogonal. Measurements were made over a wavelength of 400-700 nm. Tables 1 and 2 show average values of parallel transmittance Tp at 420 to 480 nm, average values at 520 to 590 nm, and average values at 600 to 640 nm.
- the single transmittance Ys, parallel transmittance Yp, and orthogonal transmittance Yc of each measurement sample were determined.
- the single transmittance Ys, the parallel transmittance Yp, and the orthogonal transmittance Yc are the single transmittance Ts and the parallel transmittance obtained at predetermined wavelength intervals d ⁇ (here, 5 nm) in the wavelength region of 400 to 700 nm. It is the transmittance
- the single transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc were calculated by substituting into the following formulas (I) to (III).
- P ⁇ represents a spectral distribution of standard light (C light source)
- y ⁇ represents a color matching function of two-degree visual field. The results are shown in Tables 1 and 2.
- the absolute values of a * -s and b * -s are both 5.0 or less, and a * -p and b * -p The absolute values of both are 2.0 or less, and it can be seen that the apparent hue is very neutral and paper white. Further, the parallel transmittance Tp of the measurement samples of Examples 1 to 29 had an average value at 520 to 590 nm of 25% or more.
- the parallel transmittance Tp is 1.5% or less in absolute value of the difference between the average value at 420 to 480 nm and the average value at 520 to 590 nm, and 520
- the absolute value of the difference between the average value at ⁇ 590 nm and the average value at 590 to 640 nm was 2.0% or less, and both were very low values.
- the measurement samples of Comparative Examples 1 to 5 have a lower degree of polarization ( ⁇ y) and an equivalent parallel transmittance (Yp) as compared with Examples showing equivalent single transmittance (Ys). Since Yc is higher than the example, it can be seen that the polarization function is lower than that of the example.
- ⁇ y degree of polarization
- Yp equivalent parallel transmittance
- Example 3 is 99.95%, while Comparative Example 1 is 98.15%.
- the degree of polarization of Example 3 was 1.8% higher than that of Comparative Example 1.
- the contrast (Yp / Yc) of Example 3 is 1985, whereas Comparative Example 1 has a low value of about 53, and Example 3 has a high contrast of about 37 times that of Comparative Example 1. It was.
- Example 25 is 99.61%, while Comparative Example 3 is about 95.57%.
- the degree of polarization was 4.04% higher than that of Comparative Example 3.
- the contrast (Yp / Yc) of Example 25 was 256, whereas Comparative Example 3 was about 22, and Example 25 had a high contrast of 11 times or more that of Comparative Example 3.
- Example 2 is 37.68%, while Comparative Example 2 is 33.68%.
- the Yp was 3.98% higher than that of Comparative Example 2, indicating that it was a bright polarizing plate with the same degree of polarization.
- Example 20 has Yp of 38.25%, while Comparative Example 1 has 32.72%.
- Yp was 5.53% higher than that of Comparative Example 1 at the same degree of polarization, indicating that it was a bright polarizing plate while having the same degree of polarization.
- the polarizing plates of Examples 1 to 29 can express white like a high-quality paper at the parallel position while maintaining high single transmittance and parallel transmittance, and are neutral colors by themselves. It was shown to be a hue with (neutral gray). Furthermore, it can be seen that the polarizing plates of Examples 1 to 29 have a high degree of polarization in addition to maintaining a high transmittance and exhibiting achromaticity at a parallel position.
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Abstract
Description
また、特許文献2の偏光膜は、偏光膜1枚のみを用いて測定されたUCS色空間におけるa値及びb値を絶対値2以下にして得られるものであり、偏光膜を2枚重ねた際の白表示時及び黒表示時の両方の色相において同時に無彩色を表現できるものではなく、コントラストも非常に低い。また、特許文献2の偏光膜の単体透過率の平均値は、実施例1で31.95%、実施例2で31.41%であり、低い値を示していた。このように、特許文献2の偏光膜は透過率が低いため、高透過率及び高コントラストを求められる分野、特に、液晶表示装置及び有機エレクトロルミネッセンスなどの分野では十分な性能を有するものではなかった。さらに、特許文献2の偏光膜は、主たる二色性色素としてヨウ素を用いていることから、耐久性試験後、特に、湿熱耐久性試験(例えば、85℃、相対湿度85%の環境)後に色変化が大きく、耐久性が劣っていた。
[発明1]
式(1a)又は(1b)で表されるアゾ化合物又はその塩と、式(2)で表されるアゾ化合物又はその塩とを含有する偏光素子。
(式中、Ar1は、置換基を少なくとも1つ有するフェニル基又はナフチル基を示し、Rr1からRr4は各々独立に、水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示す。)
(式中、Av1は、スルホ基及びカルボキシ基から選択される置換基を少なくとも1つ有するフェニル基又はナフチル基を示し、Rv1からRv6は、各々独立して、水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示し、Xv1は、低級アルキル、低級アルコキシ基、スルホ基、アミノ基、低級アルキルアミノ基、ヒドロキシ基、カルボキシ基、及びカルボキシエチルアミノ基からなる群から選択される置換基を少なくとも1つ有していてもよいアミノ基、フェニルアミノ基、フェニルアゾ基、ナフトトリアゾール基、又はベンゾイルアミノ基を示す。)
(式中、Ag1は置換基を有するフェニル基又はナフチル基を示し、Bg及びCgは、各々独立に、式(BC-N)又は式(BC-P)で表され、少なくとも一方が式(BC-N)を示し、Xg1は、置換基を有してもよいアミノ基、置換基を有してもよいフェニルアミノ基、置換基を有してもよいフェニルアゾ基、又は置換基を有してもよいベンゾイルアミノ基を示す。)
(式中、Rg1は水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示し、kは0~2の整数を示す。)
(Rg2及びRg3は各々独立に水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示す。)
[発明2]
少なくとも1種の式(1a)で表される化合物又はその塩と少なくとも1種の式(1b)で表される化合物又はその塩との両方を含有する、発明1に記載の偏光素子。
[発明3]
Cgが、式(BC-N)で表される発明1又は2に記載の偏光素子。
[発明4]
式(2)で表されるアゾ化合物が式(2’)で表される発明1~3のいずれかに記載の偏光素子。
(式中、Ag1及びXg1は式(2)で定義した通りであり、Rg4及びRg5は、式(BC-N)のRg1について定義した通りであり、k1及びk2は、式(BC-N)のkについて定義した通りである。)
[発明5]
式(3)で表されるアゾ化合物又はその塩をさらに含有する発明1~4のいずれかに記載の偏光素子。
(式中、Ay1は、スルホ基、カルボキシ基、ヒドロキシ基、低級アルキル基、又は低級アルコキシ基を示し、Ry1からRy4は各々独立に、水素原子、スルホ基、低級アルキル基、又は低級アルコキシ基を示し、pは1~3の整数を示す。)
[発明6]
前記偏光素子が、ポリビニルアルコール系樹脂フィルムを基材として含む発明1~5のいずれかに記載の偏光素子。
[発明7]
JIS Z 8781-4:2013に従って自然光の透過率測定時に求められるa*値及びb*値の絶対値が、
前記偏光素子単体で、ともに5.0以下であり、
前記偏光素子2枚をその吸収軸方向が互いに平行になるように重ねて配置した状態で、ともに2.0以下である、
発明1~6のいずれかに記載の偏光素子。
[発明8]
前記偏光素子2枚を吸収軸方向が互いに平行になるように重ねて測定して求められる420nmから480nmの平均透過率と、520nmから590nmの平均透過率との差の絶対値が2.5%以下であり、かつ、520nmから590nmの平均透過率と、600nmから640nmの平均透過率との差の絶対値が2.0%以下である、発明1~7のいずれかに記載の偏光素子。
[発明9]
前記偏光素子の単体透過率が35%から65%であり、
前記偏光素子2枚をその吸収軸方向が互いに平行になるように重ねて配置した状態で求められる520nmから590nmの平均透過率が25%から45%である、
発明1~8のいずれかに記載の偏光素子。
[発明10]
発明1~9のいずれかに記載の偏光素子と、前記偏光素子の片面又は両面に設けられた透明保護層とを備える偏光板。
[発明11]
発明1~9のいずれかに記載の偏光素子又は発明10に記載の偏光板を備える液晶表示装置。
本発明に係る偏光素子は、式(1a)又は(1b)で表されるアゾ化合物と、式(2)で表されるアゾ化合物と、を含有する。任意に、式(1a)で表されるアゾ化合物及び(1b)で表されるアゾ化合物の両方を含有してもよい。任意に、式(3)で表されるアゾ化合物をさらに含有してもよい。
好ましくは、偏光素子は、これらのアゾ化合物又はその塩と、上記アゾ化合物又はその塩が吸着された基材とを含む。
(式(1a’)中、Ar1、及びRr1からRr4は、式(1a)について定義された通りである。)
(式中、Arは式(1a)におけるAr1と同じものを表す。)
(式中、R1及びR2は、式(1a)におけるRr1及びRr2とそれぞれ同じものを表す。)
(式中、Arは式(1a)のAr1と同じものを表し、R1及びR2は式(1a)におけるRr1及びRr2とそれぞれ同じものを表す。)
(式中、R3及びR4は式(1a)におけるRr3及びRr4とそれぞれ同じものを表す。)
(式中、Arは式(1a)のAr1と同じものを表し、R1及びR2は式(1a)におけるRr1及びRr2とそれぞれ同じものを表し、R3及びR4は式(1a)におけるRr3及びRr4とそれぞれ同じものを表す。)
C.I.Direct Blue 34、
C.I.Direct Blue 69、
C.I.Direct Blue 70、
C.I.Direct Blue 71、
C.I.Direct Blue 72、
C.I.Direct Blue 75、
C.I.Direct Blue 78、
C.I.Direct Blue 81、
C.I.Direct Blue 82、
C.I.Direct Blue 83、
C.I.Direct Blue 186、
C.I.Direct Blue 258、
Benzo Fast Chrome Blue FG(C.I.34225)、
Benzo Fast Blue BN(C.I.34120)、
C.I.Direct Green 51、
等のアゾ化合物が挙げられる。
透過率は、JIS Z 8722:2009に従って求められる、視感度補正後の透過率である。透過率の測定は、測定試料(例えば、偏光素子又は偏光板)について、400~700nmの各波長について、5nm又は10nmごとに分光透過率を測定し、これを2度視野(C光源)により、視感度に補正することで求めることができる。
本発明の偏光素子は、特定の波長帯域間の平均透過率の差が所定の値以下であることが好ましい。平均透過率は、特定の波長帯域における透過率の平均値である。
本発明に係る偏光素子は、単体透過率が35%から65%であることが好ましい。単体透過率は、測定試料(例えば、偏光素子又は偏光板)1枚について、JIS Z 8722:2009に従って視感度に補正した透過率である。偏光板の性能としては、透過率がより高いものが求められるが、単体透過率が35%から60%であれば表示装置に用いても、違和感なく明るさを表現できる。透過率が高いほど偏光度は下がる傾向にあるため、偏光度とのバランスの観点からは、単体透過率は、37%から50%であることがより好ましく、さらに好ましくは38%から45%である。単体透過率が65%を超えると偏光度が低下する場合があるが、偏光素子の明るい透過率、又は、特定の偏光性能やコントラストを求める場合には、単体透過率が65%を超えてもよい。
偏光素子は、平行位で測定された520nmから590nmの波長帯域における平均透過率が28%から50%であることが好ましい。このような偏光素子は、表示装置に設けた際に、明るく、輝度の高い明瞭な表示装置とすることができる。520nmから590nmの波長帯域の透過率は、JIS Z 8781-4:2013において色を示す際に計算で用いる等色関数に基づく主な波長帯域の1つである。特に、520nmから590nmの各波長帯域は、等色関数に基づく最も視感度の高い波長帯域であり、この範囲における透過率が、目視で確認できる透過率と近い。このため、520nmから590nmの波長帯域の透過率を調整することが非常に重要である。平行位で測定された520nmから590nmの波長帯域の平均透過率は、より好ましくは29%から45%であり、さらに好ましくは30%から40%である。さらに、このときの偏光素子の偏光度は、80%から100%であることが好ましく、より好ましくは95%から100%、さらに好ましくは99%から100%である。偏光度は、高い方が好ましいが、偏光度と透過率との関係において、明るさを重視するか、偏光度(又はコントラスト)を重視するかにより、適した透過率及び偏光度に調整することができる。
色度a*値及びb*値は、JIS Z 8781-4:2013に従って自然光の透過率測定時に求められる値である。JIS Z 8781-4:2013に定められる物体色の表示方法は、国際照明委員会(略称:CIE)が定める物体色の表示方法に相当する。色度a*値及びb*値の測定は、測定試料(例えば、偏光素子又は偏光板)に自然光を照射して行われる。なお、以下において、測定試料1枚について求められる色度a*値及びb*値はa*-s及びb*-s、測定試料2枚をその吸収軸方向が互いに平行となるように配置した状態(白表示時)について求められる色度a*値及びb*値はa*-p及びb*-p、測定試料2枚をその吸収軸方向が互いに直交するように配置した状態(黒表示時)について求められる色度a*値及びb*値はa*-c及びb*-cと示す。
原反フィルムは、ポリビニルアルコール系樹脂を製膜することにより作製することができる。ポリビニルアルコール系樹脂は、特に限定されず、市販のものを用いてもよいし、公知の方法で合成されたものを用いてもよい。ポリビニルアルコール系樹脂は、例えば、ポリ酢酸ビニル系樹脂をケン化することにより得ることができる。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニルのほか、酢酸ビニル及びこれと共重合可能な他の単量体の共重合体などが例示される。酢酸ビニルに共重合する他の単量体としては、例えば、不飽和カルボン酸類、オレフィン類、ビニルエーテル類、及び不飽和スルホン酸類等が挙げられる。ポリビニルアルコール系樹脂のケン化度は、通常85~100モル%程度であることが好ましく、より好ましくは95モル%以である。ポリビニルアルコール系樹脂は、さらに変性されていてもよく、例えば、アルデヒド類で変性したポリビニルホルマールやポリビニルアセタールなども使用できる。またポリビニルアルコール系樹脂の重合度は、粘度平均重合度を意味し、当該技術分野において周知の手法によって求めることができ、通常1,000~10,000程度が好ましく、より好ましくは重合度1,500~6,000程度である。
以上により得られた原反フィルムに、膨潤処理を施す。膨潤処理は20~50℃の溶液に、原反フィルムを30秒から10分間浸漬させることにより行うことが好ましい。溶液は水が好ましい。延伸倍率は、1.00~1.50倍に調整することが好ましく、1.10~1.35倍に調整することがより好ましい。偏光素子を製造する時間を短縮する場合には、後述する染色処理時にも原反フィルムが膨潤するため膨潤処理を省略することもできる。
染色工程では、原反フィルムを膨潤処理して得られた樹脂フィルムにアゾ化合物を吸着及び含浸させる。膨潤工程を省略した場合には、染色工程において原反フィルムの膨潤処理を同時に行うことができる。アゾ化合物を吸着及び含浸させる処理は、樹脂フィルムに着色する工程であるため、染色工程としている。
染色工程後、次の工程に入る前に洗浄工程(以下、「洗浄工程1」とも称する。)を行うことができる。染浄工程1は、染色工程で樹脂フィルムの表面に付着した染色溶液を洗浄する工程である。洗浄工程1を行うことによって、次に処理する液中に染料が移行するのを抑制することができる。洗浄工程1では、洗浄液として一般的には水が用いられる。洗浄方法は、洗浄液に浸漬することが好ましいが、洗浄液を樹脂フィルムに塗布することによって洗浄することもできる。洗浄の時間は、特に限定されないが、好ましくは1~300秒、より好ましくは1~60秒である。洗浄工程1での洗浄液の温度は、樹脂フィルムを構成する材料(例えば、親水性高分子、ここではポリビニルアルコール系樹脂)が溶解しない温度であることが必要となる。一般的には5~40℃で洗浄処理される。ただし、洗浄工程1の工程がなくとも、性能には問題は出ないため、洗浄工程は省略することもできる。
染色工程又は洗浄工程1の後、架橋剤及び/又は耐水化剤を含有させる工程を行うことができる。樹脂フィルムに架橋剤及び/又は耐水化剤を含有させる方法は、処理溶液に浸漬することが好ましいが、処理溶液を樹脂フィルムに塗布又は塗工してもよい。処理溶液は、架橋剤及び/又は耐水化剤を少なくとも1種と、溶媒とを含む。この工程での処理溶液の温度は、5~70℃が好ましく、5~50℃がより好ましい。この工程での処理時間は30秒~6分が好ましく、1~5分がより好ましい。
染色工程、洗浄工程1、又は架橋剤及び/又は耐水化剤を含有させる工程を行った後に、延伸工程を行う。延伸工程は、樹脂フィルムを1軸に延伸することにより行う。延伸方法は湿式延伸法又は乾式延伸法のいずれでもよい。延伸倍率は、3倍以上であることが好ましく、より好ましくは4~8倍であり、特に好ましくは5~7倍である。
延伸工程を行った後には、樹脂フィルム表面に架橋剤及び/又は耐水化剤の析出、又は異物が付着することがあるため、樹脂フィルム表面を洗浄する洗浄工程(以下、「洗浄工程2」とも称する)を行うことができる。洗浄時間は1秒~5分が好ましい。洗浄方法は、樹脂フィルムを洗浄液に浸漬することが好ましいが、溶液を樹脂フィルムに塗布又は塗工によって洗浄することもできる。洗浄液としては、水が好ましい。1段で洗浄処理することもできるし、2段以上の多段処理をすることもできる。洗浄工程の溶液温度は、特に限定されないが通常5~50℃、好ましくは10~40℃である。
延伸工程又は洗浄工程2の後には、樹脂フィルムの乾燥工程を行う。乾燥処理は、自然乾燥により行うことができるが、より乾燥効率を高めるためにはロールによる圧縮やエアーナイフ、又は吸水ロール等による表面の水分除去等により行うことができ、及び/又は送風乾燥により行うこともできる。乾燥処理温度としては、20~100℃で乾燥処理することが好ましく、60~100℃で乾燥処理することがより好ましい。乾燥処理時間は例えば30秒~20分であるが、5~10分であることが好ましい。
(ii)直交位透過率について、420nmから480nmの平均透過率と520nmから590nmの平均透過率との差の絶対値が10以下となり、520nmから590nmの平均透過率と600nmから640nmの平均透過率との差の絶対値が2.0以下となる。
(iii)単体透過率が35%から65%となる。
(iv)a*値及びb*値の絶対値の各々が、偏光素子単体でともに1.0以下となり、平行位でともに2.0以下となる。
(v)直交位で測定されたa*値及びb*値の絶対値の各々が、ともに2以下となる。
(vi)平行位透過率について、520nmから590nmの平均透過率が25~45%となる。
(vii)380nmから420nmの平均透過率と420nmから480nmの平均透過率との差が15%以下、480nmから520nmの平均透過率と420nmから480nmの平均透過率との差が15%以下、480nmから520nmの平均透過率と520nmから590nmの平均透過率と差が15%以下、及び/又は640nmから780nmの平均透過率と600nmから640nmの平均透過率との差が20%以下となる。
本発明に係る偏光板は、偏光素子と、該偏光素子の片面又は両面に設けられた透明保護層とを備える。透明保護層は、偏光素子の耐水性や取扱性の向上等を目的として設けられる。
ケン化度99%以上の平均重合度2400のポリビニルアルコールフィルム(クラレ社製 VF-PS)を45℃の温水に2分浸漬し、膨潤処理を適用し延伸倍率を1.30倍とした。水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、化合物例[2-4]を0.20質量部含有した45℃の染色液に、膨潤したフィルムを4分30秒間浸漬して、フィルムにアゾ化合物を含有させた。得られたフィルムをホウ酸(Societa Chimica Larderello s.p.a.社製)20g/lを含有した40℃の水溶液に1分浸漬した。浸漬後のフィルムを、5.0倍に延伸しながら、ホウ酸30.0g/lを含有した50℃の水溶液中で5分間の延伸処理を行った。得られたフィルムを、その緊張状態を保ちつつ、25℃の水に20秒間浸漬させることにより洗浄処理した。洗浄後のフィルムを70℃で9分間乾燥させ、偏光素子を得た。この偏光素子に対して、ポリビニルアルコール(日本酢ビポバール社製 NH-26)を4%で水に溶解したものを接着剤として用いて、アルカリ処理したトリアセチルセルロースフィルム(富士写真フィルム社製 ZRD-60)をラミネートして偏光板を得た。得られた偏光板は上記偏光素子が有していた光学性能、特に単体透過率、色相、偏光度等を維持していた。この偏光板を実施例1の測定試料とした。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物としてC.I.Direct Blue 69を0.22質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物として化合物例[2-4]を0.20質量部、式(3)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例3において、アゾ化合物の含有時間を4分30秒から3分に変えた以外は同様にして、偏光板を作製した。
実施例3において、アゾ化合物の含有時間を4分30秒から2分に変えた以外は同様にして、偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物として化合物例[2-4]を0.20質量部、式(3)の化合物として化合物例[3-2](n=1が24%、n=2が71%、n=3が5%)を0.24質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例6において、アゾ化合物の含有時間を4分30秒から3分に変えた以外は同様にして、偏光板を作製した。
実施例6において、アゾ化合物の含有時間を4分30秒から2分に変えた以外は同様にして、偏光板を作製した。
実施例6において、アゾ化合物の含有時間を4分30秒から1分に変えた以外は同様にして、偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物としてC.I.Direct Blue 69を0.22質量部、式(3)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物としてC.I.Direct Blue 69を0.22質量部、式(3)の化合物として化合物例[3-2](n=1が24%、n=2が71%、n=3が5%)を0.20質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物として化合物例[2-4]を0.20質量部、C.I.Direct Yellow 28を0.22質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-13]を0.35質量部、式(2)に記載の化合物として化合物例[2-4]を0.20質量部、式(3)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-5]を0.29質量部、式(2)に記載の化合物として化合物例[2-4]を0.20質量部、式(3)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物として化合物例[2-13]を0.21質量部、式(3)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物として化合物例[2-15]を0.243質量部、式(6)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)の化合物として化合物例[1a-25]を0.32質量部、式(2)に記載の化合物として化合物例[2-23]を0.218質量部、式(3)の化合物として化合物例[3-1]を0.27質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1b)の化合物として化合物例[1b-33]を0.15質量部、式(2)の化合物として化合物例[2-4]を0.10質量部、式(3)の化合物として化合物例[3-1]を0.05質量部を用いた点及びアゾ化合物の含有時間を4分30秒から8分00秒に変えた点以外は実施例1と同様にして、偏光板を作製した
実施例18において、膨潤したフィルムを染色工程にてアゾ化合物を含有させる時間を8分から4分に変えた以外は同様にして、偏光板を作製した。
実施例19で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1b)の化合物として化合物例[1b-33]を0.15質量部、式(2)の化合物として化合物例[2-4]を0.10質量部、式(3)の化合物として化合物例[3-2](n=1が24%、n=2が71%、n=3が5%)を0.05質量部を用いた以外は実施例18と同様にして偏光板を作製した。
実施例19で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1b)の化合物として化合物例[1b-33]を0.15質量部、式(2)の化合物として化合物例[2-4]を0.10質量部、C.I.Direct Yellow 28を0.05質量部を用いた以外は実施例18と同様にして偏光板を作製した。
実施例19で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1b)の化合物として化合物例[1b-56]を0.25質量部、式(2)の化合物として化合物例[2-4]を0.10質量部、式(3)の化合物として化合物例[3-2](n=1が24%、n=2が71%、n=3が5%)を0.05質量部を用いた以外は実施例18と同様にして偏光板を作製した。
実施例19で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1b)の化合物として化合物例[1b-35]を0.22質量部、式(2)の化合物として化合物例[2-4]を0.10質量部、式(3)の化合物として化合物例[3-2](n=1が24%、n=2が71%、n=3が5%)を0.05質量部を用いた以外は実施例18と同様にして偏光板を作製した。
実施例19で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1b)の化合物として化合物例[1b-35]を0.22質量部、式(2)の化合物として化合物例[2-17]を0.10質量部、式(3)の化合物として化合物例[3-1]を0.05質量部を用いた以外は実施例18と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)に記載の化合物として化合物例[1a-25]を0.20質量部、式(1b)に記載の化合物として化合物例[1b-33]を0.15質量部、式(2)に記載の化合物として化合物例[2-17]を0.1質量部、式(3)の化合物として化合物例[3-1]を0.05質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例25において、アゾ化合物の含有時間を4分30秒から3分に変えた以外は同様にして、偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)に記載の化合物として化合物例[1a-25]を0.20質量部、式(1b)に記載の化合物として化合物例[1b-44]を0.17質量部、式(2)に記載の化合物として化合物例[2-4]を0.17質量部、式(3)の化合物として化合物例[3-1]を0.05質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)に記載の化合物として化合物例[1a-25]を0.20質量部、式(1b)に記載の化合物として化合物例[1b-56]を0.23質量部、式(2)に記載の化合物として化合物例[2-4]を0.17質量部、式(3)の化合物として化合物例[3-1]を0.05質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1で用いた染色液に代えて、水を1500質量部、トリポリリン酸ナトリウムを1.5質量部、無水芒硝を1.5質量部、式(1a)に記載の化合物として化合物例[1a-13]を0.13質量部及び式(1b)に記載の化合物として化合物例[1b-35]を0.15質量部、式(2)に記載の化合物として化合物例[2-4]を0.17質量部、式(3)の化合物として化合物例[3-1]を0.05質量部を用いた点以外は実施例1と同様にして偏光板を作製した。
実施例1においてアゾ化合物を含有する水溶液(染色液)を特許文献3の実施例1と同じ組成とし、アゾ化合物を含有させる時間(膨潤したPVAフィルムの染着槽への浸漬時間)を比較例1において12分、比較例2において10分、比較例3において8分、比較例4において5分30秒、比較例5において4分と変えた以外は、実施例1と同様にして、アゾ化合物を含有させて偏光板を作製した。
ニュートラルグレー色を有するポラテクノ社製の高透過率染料系偏光板SHC-115を入手し、測定試料とした。
ニュートラルグレー色の、高コントラストを有するポラテクノ社製の染料系偏光板SHC-128を入手し、測定試料とした。
特開2008-065222号公報の比較例1の製法に従い、ただしヨウ素含有時間を、比較例8において5分30秒、比較例9において4分45秒、比較例10において4分15秒、比較例11において3分30秒、比較例12において4分00秒、比較例13において5分15秒とし、アゾ化合物を含まないヨウ素系偏光板を作製し、測定試料とした。
平行位においてペーパーホワイト色を示すポラテクノ社製のヨウ素系偏光板SKW-18245Pを入手し、測定試料とした。
染料系偏光板に関する特開平11-218611号公報の実施例1の通りに、偏光板を作製した。
染料系偏光板に関する特開2001-033627号公報の実施例3の通りに、偏光板を作製した。
染料系偏光板に関する特開2004-251962公報の実施例1の通りに、偏光板を作製した。
0.15質量部の化合物例[2-17]に代えて、同色の二色性を有するジアニシジン骨格を有するアゾ化合物である0.29質量部のC.I.Direct Blue 6を用いて、直交位の透過率がほぼ一定で、その色が黒になるように設計した点以外は実施例25と同様にして、偏光板を作製した。
実施例1~29及び比較例1~18で得られた測定試料の評価を次のようにして行った。
(a)単体透過率Ts、平行位透過率Tp、及び直交位透過率Tc
各測定試料の単体透過率Ts、平行位透過率Tp、及び直交位透過率Tcを、分光光度計(日立製作所社製“U-4100”)を用いて測定した。ここで、単体透過率Tsは、測定試料を1枚で測定した際の各波長の透過率である。平行位透過率Tpは、2枚の測定試料をその吸収軸方向が平行となるように重ね合せて測定した各波長の分光透過率である。直交位透過率Tcは、2枚の偏光板をその吸収軸が直交するように重ね合せて測定した分光透過率である。測定は、400~700nmの波長にわたって行った。
平行位透過率Tpの420~480nmにおける平均値、520~590nmにおける平均値、及び600~640nmにおける平均値を求め、表1、2に示す。
各測定試料の単体透過率Ys、平行位透過率Yp、及び直交位透過率Ycをそれぞれ求めた。単体透過率Ys、平行位透過率Yp、及び直交位透過率Ycは、400~700nmの波長領域で、所定波長間隔dλ(ここでは5nm)おきに求めた上記単体透過率Ts、平行位透過率Tp、及び直交位透過率Tcのそれぞれについて、JIS Z 8722:2009に従って視感度に補正した透過率である。具体的には、上記単体透過率Ts、平行位透過率Tp、及び直交位透過率Tcを、下記式(I)~(III)に代入して、それぞれ算出した。なお、下記式(I)~(III)中、Pλは標準光(C光源)の分光分布を表し、yλは2度視野等色関数を表す。結果を表1、2に示す。
各測定試料の偏光度ρyを、以下の式に、平行位透過率Yp及び直交位透過率Ycを代入して求めた。その結果を表3、4に示す。
ρy={(Yp-Yc)/(Yp+Yc)}1/2×100
各測定試料について、JIS Z 8781-4:2013に従って、単体透過率Ts測定時及び平行位透過率Tp測定時の各々における色度a*値及びb*値を測定した。測定には、上記の分光光度計を使用し、透過色、反射色共に室外側から入射して測定した。光源には、C光源を用いた。結果を表3、4に示す。ここで、a*-s及びb*-s、a*-p及びb*-pは、単体透過率Ts、平行位透過率Tpのそれぞれの測定時における色度a*値及びb*値にそれぞれ対応する。
各測定試料の平行位透過率Tpの520~590nmにおける平均値と420~480nmにおける平均値との差の絶対値、及び520~590nmにおける平均値と600~640nmにおける平均値との差の絶対値を求め、表3、4示す。
実施例1~29及び比較例8~14の測定試料を、85℃、相対湿度85%RHの環境に240時間置いた。その結果、実施例1~29の測定試料は透過率や色相の変化は見られなかった。これに対し、比較例8~14は偏光度が10%以上低下し、b*-cは-10より低くなり、見た目の色として青色に変化し、特に2枚の測定試料を直交位に配置した場合には黒色が大いに青色を呈色した。特に、比較例14は、著しい透過率の向上と偏光度低下が見られた。このことから、実施例1~29の偏光板を用いた液晶表示装置は信頼性が高く、長期的に高コントラストで、かつ、高い色再現性を有する液晶表示装置になることが分かった。
Claims (11)
- 式(1a)又は(1b)で表されるアゾ化合物又はその塩と、式(2)で表されるアゾ化合物又はその塩とを含有する偏光素子。
(式中、Ar1は、置換基を少なくとも1つ有するフェニル基又はナフチル基を示し、Rr1からRr4は各々独立に、水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示す。)
(式中、Av1は、スルホ基及びカルボキシ基から選択される置換基を少なくとも1つ有するフェニル基又はナフチル基を示し、Rv1からRv6は、各々独立して、水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示し、Xv1は、低級アルキル、低級アルコキシ基、スルホ基、アミノ基、低級アルキルアミノ基、ヒドロキシ基、カルボキシ基、及びカルボキシエチルアミノ基からなる群から選択される置換基を少なくとも1つ有していてもよいアミノ基、フェニルアミノ基、フェニルアゾ基、ナフトトリアゾール基、又はベンゾイルアミノ基を示す。)
(式中、Ag1は置換基を有するフェニル基又はナフチル基を示し、Bg及びCgは、各々独立に、式(BC-N)又は式(BC-P)で表され、少なくとも一方が式(BC-N)を示し、Xg1は、置換基を有してもよいアミノ基、置換基を有してもよいフェニルアミノ基、置換基を有してもよいフェニルアゾ基、又は置換基を有してもよいベンゾイルアミノ基を示す。)
(式中、Rg1は水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示し、kは0~2の整数を示す。)
(Rg2及びRg3は各々独立に水素原子、低級アルキル基、低級アルコキシ基、又はスルホ基を有する低級アルコキシ基を示す。) - 少なくとも1種の式(1a)で表される化合物又はその塩と少なくとも1種の式(1b)で表される化合物又はその塩との両方を含有する、請求項1に記載の偏光素子。
- Cgが、式(BC-N)で表される請求項1又は2に記載の偏光素子。
- 前記偏光素子が、ポリビニルアルコール系樹脂フィルムを基材として含む請求項1~5のいずれかに記載の偏光素子。
- JIS Z 8781-4:2013に従って自然光の透過率測定時に求められるa*値及びb*値の絶対値が、
前記偏光素子単体で、ともに5.0以下であり、
前記偏光素子2枚をその吸収軸方向が互いに平行になるように重ねて配置した状態で、ともに2.0以下である、
請求項1~6のいずれかに記載の偏光素子。 - 前記偏光素子2枚を吸収軸方向が互いに平行になるように重ねて測定して求められる420nmから480nmの平均透過率と、520nmから590nmの平均透過率との差の絶対値が2.5%以下であり、かつ、520nmから590nmの平均透過率と、600nmから640nmの平均透過率との差の絶対値が2.0%以下である、請求項1~7のいずれかに記載の偏光素子。
- 前記偏光素子の単体透過率が35%から65%であり、
前記偏光素子2枚をその吸収軸方向が互いに平行になるように重ねて配置した状態で求められる520nmから590nmの平均透過率が25%から45%である、
請求項1~8のいずれかに記載の偏光素子。 - 請求項1~9のいずれかに記載の偏光素子と、前記偏光素子の片面又は両面に設けられた透明保護層とを備える偏光板。
- 請求項1~9のいずれかに記載の偏光素子又は請求項10に記載の偏光板を備える液晶表示装置。
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- 2017-10-26 CN CN201780055246.0A patent/CN109690369B/zh active Active
- 2017-10-26 WO PCT/JP2017/038698 patent/WO2018079651A1/ja active Application Filing
- 2017-10-26 KR KR1020197009493A patent/KR20190070920A/ko not_active Application Discontinuation
- 2017-10-30 TW TW106137371A patent/TWI734858B/zh active
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EP3421546A4 (en) * | 2016-02-26 | 2020-01-08 | Nippon Kayaku Kabushiki Kaisha | AZO COMPOUNDS OR SALT THEREOF AND POLARIZING FILM THEREFOR |
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TWI751418B (zh) * | 2018-05-31 | 2022-01-01 | 日商住友化學股份有限公司 | 抗反射用偏光板、光學積層體及光學積層體之製造方法 |
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JP7448477B2 (ja) | 2018-09-05 | 2024-03-12 | 日本化薬株式会社 | 偏光素子並びにそれを用いた偏光板及び光学部材等 |
WO2020230647A1 (ja) * | 2019-05-13 | 2020-11-19 | 日本化薬株式会社 | 無彩色な偏光素子、並びにこれを用いた無彩色偏光板および表示装置 |
WO2022071204A1 (ja) * | 2020-09-29 | 2022-04-07 | 日本化薬株式会社 | 偏光素子、偏光板及びそれを備える表示装置 |
WO2022071201A1 (ja) * | 2020-09-29 | 2022-04-07 | 日本化薬株式会社 | 偏光素子、偏光板及びそれを備える表示装置 |
Also Published As
Publication number | Publication date |
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CN109690369B (zh) | 2021-09-28 |
KR20190070920A (ko) | 2019-06-21 |
JPWO2018079651A1 (ja) | 2019-09-19 |
JP6889178B2 (ja) | 2021-06-18 |
TWI734858B (zh) | 2021-08-01 |
TW201823369A (zh) | 2018-07-01 |
CN109690369A (zh) | 2019-04-26 |
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