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WO2016035838A1 - Élément de polarisation, plaque de polarisation ayant ledit élément de polarisation, et dispositif d'affichage à cristaux liquides ayant ledit élément de polarisation ou ladite plaque de polarisation - Google Patents

Élément de polarisation, plaque de polarisation ayant ledit élément de polarisation, et dispositif d'affichage à cristaux liquides ayant ledit élément de polarisation ou ladite plaque de polarisation Download PDF

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Publication number
WO2016035838A1
WO2016035838A1 PCT/JP2015/075017 JP2015075017W WO2016035838A1 WO 2016035838 A1 WO2016035838 A1 WO 2016035838A1 JP 2015075017 W JP2015075017 W JP 2015075017W WO 2016035838 A1 WO2016035838 A1 WO 2016035838A1
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Prior art keywords
group
transmittance
polarizing element
formula
polarization
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English (en)
Japanese (ja)
Inventor
典明 望月
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Nippon Kayaku Co Ltd
Polatechno Co Ltd
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Nippon Kayaku Co Ltd
Polatechno Co Ltd
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Priority to JP2016546684A priority Critical patent/JP6609259B2/ja
Publication of WO2016035838A1 publication Critical patent/WO2016035838A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
    • C09B31/068—Naphthols
    • C09B31/072—Naphthols containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/30—Other polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
    • C09B33/18—Trisazo or higher polyazo dyes
    • C09B33/28—Tetrazo dyes of the type A->B->K<-C<-D
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/28—Disazo or polyazo compounds containing copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes

Definitions

  • the present invention relates to a polarizing element, a polarizing plate having the polarizing element, and a polarizing element or a liquid crystal display device having the polarizing plate, and more particularly to an achromatic dye-based polarizing element having high transmittance. is there.
  • a polarizing element is produced by adsorbing and orienting iodine or dichroic dye, which is a dichroic dye, on a polyvinyl alcohol resin film or the like.
  • this polarizing element is used in a liquid crystal display device or the like as a polarizing plate by attaching a protective film made of triacetyl cellulose or the like to at least one surface thereof through an adhesive layer.
  • a polarizing plate using iodine as a dichroic dye is called an “iodine polarizing plate”, while a polarizing plate using a dichroic dye as a dichroic dye is called a “dye polarizing plate”.
  • the dye-based polarizing plate is characterized by high heat resistance, high wet heat durability, high stability, and high color selectivity by blending.
  • such a dye-based polarizing plate has a problem that the transmittance is low, that is, the contrast is low, as compared with an iodine-based polarizing plate having the same degree of polarization. Therefore, there has been a demand for a dye-based polarizing plate that maintains a high durability, has a variety of color selectivity, and has a higher transmittance and polarization characteristics.
  • the conventional polarizing plates have two polarizing plates in which the absorption axis directions are parallel to each other (hereinafter simply referred to as “parallel position”).
  • the white color exhibits a yellowish white color when it is arranged so as to be white (hereinafter simply referred to as “when white is displayed”).
  • the conventional polarizing plates have two polarizing plates whose absorption axis directions are orthogonal to each other.
  • black display When black is displayed (hereinafter sometimes simply referred to as “black display”) in a positional relationship (hereinafter sometimes simply referred to as “orthogonal position”), black is colored blue. There was a problem to do. For this reason, there has been a demand for a polarizing plate that exhibits an achromatic white color when displaying white and an achromatic black color when displaying black. In particular, until now, there has been no polarizing element or polarizing plate having a single transmittance of 35% or more, showing achromatic white when displaying white, and showing achromatic black when displaying black.
  • Patent Documents 1 and 2 disclose techniques relating to a method for improving the chromaticity of a polarizing plate.
  • a neutral coefficient is calculated, and a polarizing plate having an absolute value of 0 to 3 is disclosed.
  • the neutral coefficient (Np) is low, the polarizing plate has parallel chromaticity obtained from JIS ⁇ Z ⁇ 8729 (equivalent to JIS ⁇ Z ⁇ 8781-4: 2013).
  • the a * value is ⁇ 2 to ⁇ 1 and the b * value is 2.5 to 4.0, it exhibits yellowish green when displaying white, and the orthogonal chromaticity is The a * value is 0 to 1, but the b * value is ⁇ 1.5 to ⁇ 4.0, which indicates that blue is displayed during black display.
  • the spectral transmittance at wavelengths of 410 nm to 750 nm is within ⁇ 30% of the average value
  • the polarizing element is prepared by adding a direct dye, a reactive dye or an acid dye in addition to iodine.
  • the absolute value of the coordinate value a and b of the color in the UCS color space is both 2 or less, the chromaticity at the time of white display and black display is expressed as an achromatic color at the same time. It wasn't possible.
  • the average value of the single transmittance is as low as 31.95% in Example 1 and 31.41% in Example 2, and is a field where high transmittance and high contrast are required (for example, In fields such as liquid crystal display devices and organic electroluminescence), the performance has not been satisfactory.
  • a polarizing plate having a high transmittance for example, a single transmittance of 40% or more has not been obtained.
  • a polarizing element using iodine as a main dichroic dye has a large color change after a durability test, particularly after a wet heat durability test. As a polarizing element or polarizing plate, sufficient durability has not been obtained yet.
  • the present inventor is a polarizing element comprising a base material containing an azo compound as a constituent component, and has a single transmittance of 35% to 80%.
  • JIS Z 8781- 4 The absolute values of the chromaticity a * value and b * value obtained when measuring the transmittance of natural light according to 4: 2013 are both 1 or less for the polarizing element alone, and the two polarizing elements have mutually different absorption axis directions.
  • Polarized light characterized in that both are 2 or less in a state where they are arranged in parallel, and both are 2 or less in a state where the two polarizing elements are arranged so that their absorption axis directions are orthogonal to each other. It was newly found that the element can express achromatic white in black display and achromatic black in black display even when the transmittance is high, and has high durability.
  • the present invention “[1] A polarizing element comprising a substrate containing an azo compound as a constituent component,
  • the single transmittance is 35% to 80%
  • the absolute values of the chromaticity a * value and b * value obtained when measuring the natural light transmittance according to JIS Z 8781-4: 2013 are:
  • the polarizing elements alone are both 1 or less, In a state where the two polarizing elements are arranged so that the absorption axis directions thereof are parallel to each other, both are 2 or less, and A polarizing element characterized in that both of the polarizing elements are 2 or less in a state where the absorption axis directions are orthogonal to each other.
  • the average transmittance is measured in a plurality of wavelength regions.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 4% or less, the average transmittance of 600 nm to 670 nm, and the average transmittance of 550 nm to 600 nm.
  • the absolute value of the difference from the rate is 3% or less
  • the transmittance of each wavelength measured by irradiating absolute polarized light so that the vibration direction of light is parallel to the absorption axis direction of the polarizing element is compared with the average transmittance in a plurality of wavelength regions.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 2% or less, the average transmittance of 600 nm to 670 nm, and the average transmittance of 550 nm to 600 nm.
  • the polarizing element according to the above [1], wherein the absolute value of the difference between and is 2 or less.
  • the azo compound includes a compound represented by the following formula (1) or a salt thereof in the form of a free acid and a compound represented by the following formula (2) or a salt thereof in the form of a free acid.
  • the polarizing element according to [1] or [2]. (In the formula, A 1 represents a phenyl group or naphthyl group having a substituent, and R 1 and R 2 are each independently a lower group having a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, or a sulfo group.
  • R 3 to R 6 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, a lower alkoxy group having a sulfo group, a carbonyl group, or a halogen atom.
  • R 3 to R 6 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, a lower alkoxy group having a sulfo group, a carbonyl group, or a halogen atom.
  • a 2 and A 3 each independently represent at least one substituent having a sulfo group, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, a carboxy group, a nitro group, an amino group, or a substituent.
  • An amino group is a naphthyl group or a phenyl group
  • R 7 and R 8 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, or a lower alkoxy group having a sulfo group.
  • the azo compound comprises a compound represented by the formula (1) or a salt thereof, a compound represented by the formula (2) or a salt thereof, and a compound represented by the formula (3) or a salt thereof.
  • a 4 represents a nitro group or an amino group
  • R 9 represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a sulfo group, or a lower alkoxy group having a sulfo group
  • X 2 represents a substituted group.
  • a phenylamino group which may have a group is shown.
  • R 10 and R 11 each independently represent a sulfo group, a carboxy group, a hydroxy group, a lower alkyl group, or a lower alkoxyl group, and n represents an integer of 1 to 3)
  • a 1 in the formula (1) is a phenyl group having a substituent.
  • a 4 in the formula (4) is a nitro group.
  • the single transmittance is 35% to 60%,
  • ⁇ y min1 represents the minimum degree of polarization
  • Ys represents the single transmittance.
  • the single transmittance is more than 60% and 80% or less, The polarized light according to any one of [1] to [12], which has a polarization degree ⁇ y equal to or greater than a value of a minimum polarization degree ⁇ y min2 obtained by substituting the single transmittance in the formula (II) shown below. element.
  • ⁇ y min2 represents the minimum degree of polarization
  • Ys represents the single transmittance.
  • a liquid crystal display device comprising the polarizing element according to any one of [1] to [14] or the polarizing plate according to claim 15. ".
  • the present invention even when the transmittance is high, it is possible to obtain an achromatic white color during a white display and an achromatic black color during a black display, and it is possible to obtain a polarizing element and a polarizing plate having higher durability. .
  • FIG. 1 is an example of the intensity of reflected light of each wavelength at an electrode of a reflective liquid crystal.
  • the polarizing element according to the present invention comprises a base material containing an azo compound as a constituent component, and has a single transmittance of 35% to 80%, and is a color required when measuring the transmittance of natural light according to JIS Z 8781-4: 2013.
  • the absolute values of the degree a * value and the b * value are both 1 or less for the polarizing element alone, and both are 2 or less in a state where the two polarizing elements are arranged so that their absorption axis directions are parallel to each other.
  • the two polarizing elements are arranged so that the absorption axis directions thereof are orthogonal to each other, and both are 2 or less.
  • a polarizing element even if it has a high transmittance, it is possible to express achromatic white when displaying white and achromatic black when displaying black, and also having a high degree of polarization and high durability. An element and a polarizing plate are obtained.
  • the chromaticity a * value and b * value are values obtained when measuring the natural light transmittance 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 (abbreviated as CIE).
  • CIE International Commission on Illumination
  • Such measurement of the chromaticity a * value and b * value is performed 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.
  • Chromaticity a * value and b * value 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 orthogonal to each other (black display)
  • the chromaticity a * value and b * value obtained for (time) are denoted as a * -c and b * -c.
  • the absolute values of a * -s and b * -s are both 1 or less, and a * -p and b * -p and a * -c and b * -c Each absolute value is 2 or less. According to such a polarizing element, it is possible to realize a polarizing element and a polarizing plate that can express achromatic white during white display and achromatic black during black display.
  • the absolute values of a * -p, b * -p, a * -c and b * -c are each preferably 1.5 or less, and more preferably 1.0 or less.
  • the transmittance of each wavelength of the polarizing element is preferably controlled to a predetermined relationship.
  • the average transmittance in a plurality of wavelength regions When the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 4% or less, the average transmittance of 600 nm to 670 nm and the average transmittance of 550 nm to 600 nm
  • the absolute value of the difference from the rate is 3% or less, and the transmission of each wavelength measured by irradiating the absolute polarized light so that the vibration direction of the light is parallel to the absorption axis direction of the polarizing element.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 2% or less, and As the absolute value of the difference between 00nm to average transmittance of 670nm and 550nm to 600nm average transmission becomes 2 or less, it is preferable to control the transmittance.
  • “absolutely polarized light” means light after polarization that has passed through a polarizing plate having a degree of polarization of almost 100%, and means almost 100% of polarized light. To do.
  • the transmittance of each wavelength measured by irradiating absolute polarized light so that the vibration direction of light is orthogonal to the absorption axis direction of the polarizing element is averaged in a plurality of wavelength ranges.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 2% or less, the average transmittance of 600 nm to 670 nm and the average transmittance of 550 nm to 600 nm It is desirable to control so that the absolute value of the difference from the average transmittance is 2% or less.
  • the transmittance of each wavelength measured by irradiating absolute polarized light so that the vibration direction of light is orthogonal to the absorption axis direction of the polarizing element is averaged in a plurality of wavelength ranges.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 1.5% or less, and the average transmittance of 600 nm to 670 nm is compared to 550 nm to 600 nm.
  • the absolute value of the difference from the average transmittance is 1.5% or less, and further measured by irradiating with absolute polarized light so that the vibration direction of light is parallel to the absorption axis direction of the polarizing element.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 1. % Or less A, and it is desirable that the absolute value of the difference between 600nm to average transmittance of 670nm and 550nm to 600nm average transmission is controlled to be 1.5% or less.
  • the single transmittance is a single transmittance Ys after visibility correction, which is obtained in accordance with JIS Z 8722: 2009.
  • the single transmittance Ys is measured by measuring the spectral transmittance Ts every 5 nm or 10 nm for each wavelength of 400 to 700 nm for one measurement sample (for example, polarizing element or polarizing plate), and measuring this twice. It can be obtained by correcting the visibility with the field of view (C light source).
  • the polarizing element according to the present invention has a single transmittance Ys of 35% to 80%.
  • the performance of the polarizing plate is required to be higher, but if the single transmittance Ys is 35% to 80%, the brightness can be expressed without a sense of incompatibility even if it is used in a display device.
  • the single unit transmittance Ys is preferably 38% to 55%, more preferably 40% to 55% from the viewpoint of balance with the degree of polarization. 55%.
  • the polarizing element according to the present invention can improve visibility. That is, the polarizing element of the present invention can make white when displaying white and black when displaying black, achromatic, depending on the presence or absence of polarized light, can express white and black clearly, and improves the brightness due to its high transmittance. Can be made. Therefore, the visibility is improved by the clear difference in the brightness, and the visibility is good depending on the display.
  • the degree of polarization is preferably 10% or more, more preferably 20% or more, and further 30% or more.
  • a display in which reflection is actually desired for example, a display such as a reflective liquid crystal display or an OLED
  • the polarizing element has a degree of polarization that can control reflection at the time of display.
  • Such a polarizing element can be used for a display having high luminance or high reflectance. Can be designed. Therefore, even a polarizing element having a single transmittance of more than 60% and 80% or less can be effectively used.
  • the polarizing plate is required to have a higher degree of polarization.
  • the polarization degree of the polarizing element (hereinafter sometimes referred to as “ ⁇ y”) is preferably 50% or more. More preferably, it is 75% or more, more preferably 90% or more, and particularly preferably 99% or more.
  • the degree of polarization ⁇ y of the polarizing element according to this embodiment is expressed by the following formula (I) when the single transmittance Ys (hereinafter sometimes simply referred to as “Ys”) is 35% to 60%.
  • Is preferably not less than the numerical value of the minimum polarization degree ⁇ y min1 obtained by substituting the single transmittance Ys, and when the single transmittance Ys is more than 60% and 80% or less, the following formula is shown: It is preferable to be not less than the numerical value of the minimum polarization degree ⁇ y min2 obtained by substituting the single transmittance Ys for (II).
  • the polarizing element of the present invention has a polarization degree equal to or greater than the minimum polarization degree ⁇ y min1 or the minimum polarization degree ⁇ y min2 , and thus can maintain a high degree of polarization with respect to the transmittance even when the transmittance is high. it can.
  • Ys is the single transmittance (actually measured value) of the polarizing element
  • ⁇ y min1 is the preferred minimum polarization with a degree of polarization when the single transmittance Ys is 35% to 60%.
  • Degree (threshold) is a preferable minimum degree of polarization (threshold) when the single transmittance Ys is more than 60% and 80% or less.
  • the polarization degree ⁇ y of the polarizing element according to this embodiment is the minimum obtained by substituting the single transmittance Ys into the following formula (III) when the single transmittance Ys is 35% to 60%. More preferably, the degree of polarization ⁇ y min3 is greater than or equal to the numerical value. When the single transmittance Ys is more than 60% and 80% or less, it is obtained by substituting the single transmittance Ys into the following formula (IV). It is more preferable that the value be equal to or greater than the value of the minimum polarization degree ⁇ y min4 .
  • Ys is the single transmittance (measured value) of the polarizing element
  • ⁇ y min3 is a more preferable minimum of the degree of polarization when the single transmittance Ys is 35% to 60%. It is a degree of polarization (threshold), and ⁇ y min4 is a more preferable minimum degree of polarization (threshold) when the single transmittance Ys is more than 60% and 80% or less.
  • the polarizing element of the present invention comprises a substrate containing an azo compound as a constituent component.
  • the azo compound is preferably a dichroic dye.
  • the dichroic dye made of an azo compound for example, an organic compound as shown in Non-Patent Document 1 can be used. In particular, those having high dichroism are preferable. For example, Sea. Ai. direct. Yellow 12, sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, sea. Ai. direct. Orange 107, sea. Ai. direct. Red 2, sea. Ai. direct. Red 31, sea. Ai. direct.
  • Examples thereof include Green 59, and organic dyes described in JP-A Nos. 2001-33627, 2002-296417, and 60-156759. These organic dyes can be used as free metal, alkali metal salt (for example, Na salt, K salt, Li salt), ammonium salt, or amine salt. However, a dichroic dye is not limited to these, A well-known dichroic dye can also be used.
  • the azo compound is preferably a dye comprising a free acid, a salt thereof or a metal complex salt thereof. In these cases, optical properties are particularly improved.
  • the metal complex is not particularly limited, but is preferably a transition metal complex, and particularly preferably a copper complex.
  • the dye containing an azo compound may be used only by 1 type, may be mix
  • the polarizing element of this invention is realizable by adjusting the transmittance
  • the azo compound contains a compound represented by the following formula (1) or a salt thereof in the form of a free acid and a compound represented by the following formula (2) or a salt thereof in the form of a free acid.
  • an azo compound contains the compound or its salt shown by following formula (1) in the form of a free acid, and the compound or its salt shown by following formula (3) in the form of a free acid. According to the base material toned with such an azo compound, it is possible to obtain a polarizing element capable of expressing white at the time of white display and black at the time of black display more achromatic.
  • a 1 represents a phenyl group or naphthyl group having a substituent
  • R 1 and R 2 each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, or a sulfo group
  • X 1 represents a phenylamino group which may have a substituent.
  • a 1 is preferably a phenyl group having a substituent.
  • substituents include, for example, a sulfo group, a carbonyl group, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a lower alkyl group having a sulfo group, and an alkoxyl group having a sulfo group. Or it is more preferable that it is a carbonyl group.
  • the number of substituents as described above may be one, or may be two or more. In the present specification, “lower” in the lower alkyl group and the lower alkoxy group means 1 to 3 carbon atoms.
  • R 3 to R 6 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, a lower alkoxy group having a sulfo group, a carbonyl group, or a halogen atom.
  • a 2 and A 3 are each independently a lower alkoxy group having at least one of a substituent having a sulfo group, a lower alkyl group, a lower alkoxy group, or a sulfo group, a carboxy group, a nitro group, an amino group.
  • a naphthyl group or a phenyl group which is a group or a substituted amino group, and R 7 and R 8 each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, or a lower alkoxy group having a sulfo group. Show.
  • a 2 and A 3 are naphthyl groups having a sulfo group or a carbonyl group. It is preferable. In particular, a case having a sulfo group is preferable, and high contrast can be realized in a polarizing element or a polarizing plate.
  • the azo compound according to this embodiment preferably further contains a compound represented by the following formula (4) in the form of a free acid, a salt thereof or a metal complex thereof.
  • a white light at the time of white display and a black color at the time of black display can be expressed in a more achromatic color, and a polarizing element having higher transmittance and degree of polarization can be obtained. It is done.
  • the metal complex is not particularly limited, but is preferably a transition metal complex, and particularly preferably a copper complex.
  • a 4 represents a nitro group or an amino group
  • R 9 represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, a sulfo group, or a lower alkoxy group having a sulfo group
  • X 2 represents a phenylamino group which may have a substituent.
  • a 4 is preferably a nitro group
  • R 9 is a methoxy group.
  • the polarization performance is improved when A 4 is a nitro group.
  • the azo compound preferably further contains a compound represented by the following formula (5) in the form of a free acid, a salt thereof or a metal complex thereof.
  • a white light at the time of white display and a black color at the time of black display can be expressed in a more achromatic color, and a polarizing element having higher transmittance and degree of polarization can be obtained. It is done.
  • the metal complex is not particularly limited, but is preferably a transition metal complex, and particularly preferably a copper complex.
  • R 10 and R 11 each independently represent a sulfo group, a carboxy group, a hydroxy group, a lower alkyl group, or a lower alkoxyl group, and n represents an integer of 1 to 3.
  • R 10 and R 11 are preferably a sulfo group or a carbonyl group.
  • R 10 and R 11 are a sulfo group or a carbonyl group, a polarizing element capable of expressing white at the time of white display and black at the time of black display more achromatic is obtained.
  • the terminal substituents are preferably different.
  • the polarization degree of the polarizing element on the short wavelength side particularly the polarization degree of 400 nm to 480 nm is improved, and b * -p or b * -c of the polarizing plate is closer to zero. , Closer to achromatic.
  • the compound represented by the above formula (1) or a salt thereof More preferably, the compound represented by the above formula (2) or a salt thereof and the compound represented by the above formula (3) or a salt thereof are simultaneously contained.
  • Examples of the method for obtaining the compound represented by the above formula (1) include Japanese Patent Application Laid-Open No. 2003-215338, Japanese Patent Application Laid-Open No. 9-302250, Japanese Patent No. 3881175, Japanese Patent No. 4462237, and Japanese Patent No. 4662853. However, it is not limited to these methods. Below, the specific example of the azo compound represented by the said Formula (1) is shown in the form of a free acid.
  • the compound represented by the above formula (2) can be produced by performing coupling in accordance with an ordinary azo dye production method as described in Non-Patent Document 2.
  • an amino compound represented by the following formula (6) is diazotized by a known method, and N, N-bis (1-hydroxy-3-sulfo-6-naphthyl) amine (conventional) is used. (Name: di-J acid) at 10 to 20 ° C. to obtain a disazo compound.
  • the obtained disazo compound is added with, for example, copper sulfate, aqueous ammonia, amino alcohol and hexamethylenetetramine, and subjected to a copperation reaction at 85 to 95 ° C. to obtain a solution containing the compound of the above formula (2).
  • the compound of the above formula (2) can be obtained by evaporating this solution to dryness, or salting out, drying, pulverizing and pulverizing.
  • Rx and Ry represent the same meaning as R 3 to R 6 in the formula (2).
  • Examples of the method for obtaining the compound represented by the above formula (3) include, but are not limited to, the methods described in International Publication No. 2012/165223. Below, the specific example of the azo compound represented by the said Formula (3) is shown in the form of a free acid.
  • examples of the method for obtaining the compound represented by the above formula (5) include methods described in International Publication No. 2007/138980, but are not limited thereto.
  • examples of the azo compound represented by the above formula (5) include dyes described in International Publication No. 2007/138980, C.I. I. Direct Yellow 4, C.I. I. Direct Yellow 12, C.I. I. Direct Yellow 72, C.I. I. An azo compound having a stilbene structure such as Direct Orange 39 can be preferably used.
  • the specific example of the azo compound represented by the said Formula (5) is shown in the form of a free acid.
  • the method for obtaining a substrate containing an azo compound is not particularly limited.
  • an azo compound is used as a constituent component by impregnation or coating on the surface or inside of a material previously formed into a film shape.
  • the method of making it contain, the method of shape
  • the material containing the azo compound is not particularly limited, and examples thereof include a hydrophilic polymer that can generally contain a dichroic dye.
  • Such hydrophilic polymers are not particularly limited, and examples thereof include polyvinyl alcohol resins, amylose resins, starch resins, cellulose resins, and polyacrylate resins.
  • a resin comprising a polyvinyl alcohol-based resin and a derivative thereof is most preferable from the viewpoints of processability, dyeability, crosslinkability, and the like.
  • a material is formed into a film shape, and a substrate containing the azo compound according to the present invention can be obtained by incorporating the dye and the compound thereof as described above by orientation treatment such as stretching. it can.
  • a specific method for producing a polarizing element will be described by taking as an example the case of producing a substrate containing an azo compound using a polyvinyl alcohol resin.
  • the manufacturing method of the polarizing element which concerns on this invention is not limited to the following manufacturing method.
  • a polyvinyl alcohol-type resin is not specifically limited, A commercially available thing may be used and what was synthesize
  • the polyvinyl alcohol-based resin can be obtained, for example, by saponifying a polyvinyl acetate-based 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 more.
  • a polyvinyl alcohol-based 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 1000 to 10,000, more preferably about 1500 to 6000. is there.
  • a polyvinyl alcohol-based resin is formed into a raw film.
  • the method for forming a 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 weight, more preferably 8 to 15% by weight based on the whole film.
  • the film thickness of the raw film made of polyvinyl alcohol resin is not particularly limited, but is preferably about 5 ⁇ m to 150 ⁇ m, for example, and more preferably about 10 ⁇ m to 100 ⁇ m.
  • the swelling treatment is preferably performed by immersing the original film in a solution at 20 ° C. 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.
  • a swelling process can also be abbreviate
  • a dyeing step is performed.
  • the resin film after the treatment is impregnated with an azo compound. Since the treatment for impregnating the azo compound in this manner is a step of coloring the resin film, it is a dyeing step.
  • an azo compound which is a dichroic dye described in Non-Patent Document 1 Formula (1), Formula (2), Formula (3), Formula (4), Formula (5), etc.
  • the azo compound shown by can be used.
  • These azo compounds are used as free acids and may be salts of these compounds.
  • alkali metal salts such as lithium salts, sodium salts and potassium salts, and organic salts such as ammonium salts and alkylamine salts can be used, and sodium salts are preferable.
  • the dyeing step is preferably performed by immersing the resin film in a dyeing solution containing the azo compound, for example.
  • the dyeing method is not particularly limited as long as it is a method of adsorbing and impregnating an azo compound to the resin film, but it is preferable to immerse the resin film in a dyeing solution, and to apply the dyeing solution to the resin film. You can also.
  • 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 content of the azo compound in such a dyeing solution can be arbitrarily adjusted depending on the dyeing property of the dye containing the azo compound, the dyeing time and the temperature, etc., but preferably 0.001 to 10% by weight of the whole solution Is preferable, and 0.01 to 1% by weight is more preferable.
  • such a dyeing solution may contain sodium carbonate, sodium hydrogen carbonate, sodium chloride, sodium sulfate, anhydrous sodium sulfate, sodium tripolyphosphate, and the like as a dyeing aid.
  • Their content can be adjusted at an arbitrary concentration depending on the time and temperature depending on the dyeability of the dye, but each content is preferably 5% by weight or less, more preferably 0.1 to 2% by weight of the whole solution. .
  • washing step 1 is a step of washing the dye solvent adhering to the surface of the resin film in the dyeing step.
  • the washing step 1 water is generally used as a solvent.
  • the cleaning method it is preferable to immerse the resin film in the solution, but the cleaning can also be performed by applying the solution to the 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 solvent in the washing step 1 needs to be a temperature at which a material constituting the resin film (for example, a hydrophilic polymer, here, a polyvinyl alcohol resin) does not dissolve. Generally, it is washed at 5 to 40 ° C. However, since there is no problem in performance even without the cleaning step 1, this step can be omitted.
  • a material constituting the resin film for example, a hydrophilic polymer, here, a polyvinyl alcohol resin
  • Step of containing at least one of 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 crosslinking agent include boron compounds such as boric acid, borax or ammonium borate, polyhydric aldehydes such as glyoxal or glutaraldehyde, polyhydric isocyanate 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.
  • succinic peroxide As the water-proofing agent, succinic peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride or magnesium chloride can be used, preferably boric acid. Is used.
  • the step of containing a crosslinking agent and / or a water-resistant agent is performed using at least one or more crosslinking agents and / or a water-resistant agent as described above.
  • water is preferable as the solvent, but it is not limited.
  • concentration of the cross-linking agent and / or the water-proofing agent in the solvent in the step of containing the cross-linking agent and / or the water-proofing agent is 0.1 to 6. 0% by weight is preferable, and 1.0 to 4.0% by weight is more preferable.
  • the solvent temperature in this step is preferably 5 to 70 ° C, more preferably 5 to 50 ° C.
  • the method of incorporating a crosslinking agent and / or a water resistance agent into the resin film is preferably immersed in the solution, but the solution may be applied or applied to the resin film.
  • the treatment time in this step is preferably 30 seconds to 6 minutes, more preferably 1 to 5 minutes.
  • this treatment step may be omitted if a crosslinking treatment or a water-resistant treatment is unnecessary. Good.
  • the stretching process is a step of stretching the resin film uniaxially.
  • the stretching method may be either a wet stretching method or a dry stretching method.
  • the stretching ratio is preferably 3 times or more, more preferably 5 to 7 times.
  • the stretching heating medium is an air medium
  • the temperature of the air medium is preferably stretched at a room temperature to 180 ° C.
  • the treatment is preferably performed 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, an infrared heating stretching method, and the like, 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 wet stretching method it is preferable to stretch in water, a water-soluble organic solvent, or a mixed solution thereof. Furthermore, it is more preferable to perform the stretching treatment while being immersed in a solution containing a crosslinking agent and / or a water resistance agent.
  • crosslinking agent examples include boron compounds such as boric acid, borax or ammonium borate, polyhydric aldehydes such as glyoxal or glutaraldehyde, polyhydric isocyanate 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
  • polyhydric aldehydes such as glyoxal or glutaraldehyde
  • polyhydric isocyanate 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.
  • succinic peroxide As the water-resistant agent, succinic peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride, magnesium chloride, or the like can be used. It is preferable to perform stretching in a solution containing at least one or more crosslinking agents and / or water resistance agents as described above, and it is particularly preferable to contain boric acid as a crosslinking agent.
  • the concentration of the crosslinking agent and / or waterproofing agent in the stretching step is, for example, preferably from 0.5 to 15% by weight, more preferably from 2.0 to 8.0% by weight based on the solution.
  • the draw ratio is preferably 2 to 8 times, more preferably 5 to 7 times.
  • the stretching temperature is preferably 40 to 60 ° C, more preferably 45 to 58 ° 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, since the precipitation of the crosslinking agent and / or waterproofing agent or foreign matter may adhere to the resin film surface, a cleaning process for cleaning the resin film surface (hereinafter referred to as cleaning process 2) is performed. be able to.
  • the washing time is preferably 1 second to 5 minutes.
  • the cleaning method it is preferable to immerse the resin film in a cleaning solution, but the cleaning may be performed by applying or applying the cleaning solution to the resin film.
  • 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.
  • the solvent used in the treatment steps so far includes, in addition to water, for example, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol. , Alcohols such as tetraethylene glycol or trimethylolpropane, amines such as ethylenediamine or diethylenetriamine, and the like, but are not limited thereto. These solvents can be used alone, but two or more kinds may be mixed and used. The most preferred solvent is water.
  • the drying treatment can be performed by natural drying, but in order to further increase the drying efficiency, it can be performed by compression with a roll, removal of moisture on the surface with an air knife or a water absorption roll, etc. It can also be performed by blow drying.
  • the drying treatment temperature is preferably 20 to 100 ° C., more preferably 60 to 100 ° C.
  • a drying treatment time of 30 seconds to 20 minutes can be applied, but 5 to 10 minutes is preferable.
  • a polarizing element having a predetermined single transmittance and chromaticity which is a base material containing a dichroic dye made of an azo compound, can be obtained.
  • the polarizing plate of the present invention can be obtained by providing a transparent protective layer on at least one surface of the polarizing element of the present invention.
  • the polarizing plate may be provided with a transparent protective layer on both surfaces of the polarizing element.
  • the transparent protective layer can be provided as a polymer coating layer or as a film laminate layer.
  • the transparent polymer or film forming the transparent protective layer is preferably a transparent polymer or film having high mechanical strength and good thermal stability.
  • substances used as the transparent protective layer include cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyvinyl chloride resins, nylon resins, polyester resins, polyarylate resins, and cyclic olefins such as norbornene. Cyclic polyolefin resins, polyethylene, polypropylene, polyolefins having a cyclo or norbornene skeleton or copolymers thereof, resins or polymers having imides and / or amides in the main chain or side chains, or films thereof. In addition, a resin having liquid crystallinity or a film thereof can be provided as the transparent protective layer.
  • the thickness of the transparent protective layer is, for example, about 0.5 to 200 ⁇ m.
  • a polarizing plate is produced by providing one or more layers of the same or different types of resins or films on one side or both sides.
  • An adhesive is required for the transparent protective layer to be bonded to the polarizing element of the present invention.
  • a polyvinyl alcohol adhesive agent is preferable.
  • the polyvinyl alcohol 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.
  • As the polyvinyl alcohol adhesive a maleic anhydride-isobutylene copolymer is used, but if necessary, an adhesive mixed with a crosslinking agent can be used.
  • maleic anhydride-isobutylene copolymers for example, isoban # 18 (manufactured by Kuraray), isoban # 04 (manufactured by Kuraray), ammonia-modified isoban # 104 (manufactured by Kuraray), ammonia-modified isoban # 110 (manufactured by Kuraray) ), Imidized isoban # 304 (manufactured by Kuraray), imidized isoban # 310 (manufactured by Kuraray), and the like.
  • a water-soluble polyvalent epoxy compound can be used as the crosslinking agent at that time.
  • the water-soluble polyvalent epoxy compound examples include Denacol EX-521 (manufactured by Nagase Chemtech) and Tetrat-C (manufactured by Mitsui Gas Chemical Co., Ltd.).
  • adhesives other than polyvinyl alcohol resin well-known adhesives, such as a urethane type, an acrylic type, and an epoxy type, can also be used.
  • additives such as zinc compounds, chlorides and iodides can be simultaneously contained at a concentration of about 0.1 to 10% by weight. The additive is not limited.
  • the viewing angle is improved on the surface of the protective layer or film that will later become an unexposed surface and / or Various functional layers for improving contrast, and a layer or film having brightness enhancement can also be provided.
  • a layer or film having brightness enhancement can also be provided.
  • an adhesive In order to attach the polarizing plate to these films and display devices, it is preferable to use an adhesive.
  • This polarizing plate may have various known functional layers such as an antireflection layer, an antiglare layer, and a hard coat layer on the protective layer or the exposed surface of the 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 various functional layers can be a layer or a film for controlling the phase difference.
  • the polarizing element or polarizing plate of the present invention can be suitably used for a liquid crystal display device or the like.
  • the liquid crystal display device using the polarizing element or polarizing plate of the present invention is highly reliable, has a long-term high contrast, and has a high color reproducibility.
  • the reflective liquid crystal uses a transparent electrode such as ITO (Indium tin Oxide), an aluminum electrode, or the like as the material of the drive electrode
  • the reflected light of the electrode reflects each wavelength as shown in FIG. It shows intensity, and its reflected color is green.
  • the reflected light intensity shown in FIG. 1 is a result of measurement using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.) and converting the highest reflected light intensity as 100.
  • the value of the a * value obtained by measuring the two polarizing elements in a state where their absorption axis directions are parallel to each other is adjusted, It is more preferable that the color is slightly red.
  • a preferable range of the a * value obtained by measuring two polarizing elements in a state where their absorption axis directions are parallel to each other is ⁇ 0.5 to 1.7, more preferably 0 to 1. .5, more preferably 0.3 to 1.2.
  • the polarizing element or polarizing plate of the present invention thus obtained is provided with a protective layer or a functional layer and a support as necessary, and a liquid crystal projector, a calculator, a watch, a notebook computer, a word processor, a liquid crystal television, a polarizing lens, and polarizing glasses. Used for car navigation and indoor / outdoor measuring instruments and displays. In particular, it is used as an effective polarizing element or polarizing plate in reflective liquid crystal display devices, transflective liquid crystal display devices, organic electroluminescence, and the like.
  • the polarizing plate of the present invention may be used as a polarizing plate with a support.
  • the support preferably has a flat portion, and since it is used for optical purposes, a glass molded product is preferable.
  • the glass molded product include a glass plate, a lens, and a prism (for example, a triangular prism and a cubic prism).
  • a lens attached with a polarizing plate can be used as a condenser lens with a polarizing plate in a liquid crystal projector.
  • a prism attached with a polarizing plate can be used as a polarizing beam splitter with a polarizing plate or a dichroic prism with a polarizing plate in a liquid crystal projector.
  • the material of the glass include inorganic glass such as soda glass, borosilicate glass, inorganic base made of quartz, inorganic base made of sapphire, and organic plastic plates such as acrylic and polycarbonate. Is preferred.
  • the glass plate may have a desired thickness and size. In order to further improve the single plate light transmittance, it is preferable to provide an AR layer on one or both of the glass surface and the polarizing plate surface of the polarizing plate with glass.
  • a transparent adhesive (adhesive) agent is applied to the flat surface of the support, and then the polarizing plate of the present invention is attached to the coated surface.
  • a transparent adhesive (adhesive) agent may be applied to the polarizing plate, and then a support may be attached to the coated surface.
  • the adhesive (adhesive) agent used here is preferably, for example, an acrylic ester-based one.
  • this polarizing plate as an elliptical polarizing plate, it is normal to stick the phase difference plate side to a support body side, but you may affix a polarizing plate side to a glass molded product.
  • Dye (1) A dye containing an azo compound having the chemical structure of the above formula (1). It produced according to Example 1 of the patent 4033443 gazette.
  • Dye (2) A dye containing an azo compound having the chemical structure of the above formula (2). It was produced by the method shown in Synthesis Example 1 below.
  • Dye (3) A dye containing an azo compound having the chemical structure of the above formula (3). It manufactured according to the synthesis example 1 of international publication 2012/165223.
  • Dye (4) A dye containing an azo compound having the chemical structure of the above formula (4). Manufactured according to Example 3 of JP2013-057909A.
  • Dye (5) a dye containing an azo compound having the chemical structure of the above formula (5). C. which is a commercial product. I. Direct Orange 39 (Nippon Kayaku Kayara Supra Orange 2GL) was used.
  • Example 1 A polyvinyl alcohol film (VF-PS, manufactured by Kuraray Co., Ltd.) having a thickness of 40 ⁇ m, a saponification degree of 99% or more and an average polymerization degree of 2400 is immersed in warm water at 45 ° C. for 2 minutes, and a swelling treatment is applied. 30 times.
  • VF-PS polyvinyl alcohol film
  • the swelled film was mixed with 1500 parts by weight of water syrup, 1.5 parts by weight of sodium tripolyphosphate (manufactured by Junsei Chemical Co., Ltd.), 1.5 parts by weight of anhydrous sodium sulfate (manufactured by Junsei Kagaku), Dip (2) 0.17 parts by weight, dye (4) 0.105 parts by weight and dye (5) 0.13 parts by weight in an aqueous solution mixed with 0.13 parts by weight at 45 ° C. for 3 minutes 00 seconds. Dye was included (dyeing process).
  • the obtained film was immersed in a 20.0 g / l aqueous solution of boric acid (manufactured by Societa Chimerica Ladderello spa) at 40 ° C. for 1 minute.
  • the film was immersed in a 30.0 g / l boric acid aqueous solution at 50 ° C. for 5 minutes and stretched.
  • the film was immersed in a 20.0 g / l aqueous solution of potassium iodide (manufactured by Junsei Chemical Co., Ltd.) at 30 ° C. for 20 seconds while maintaining the tension state of the obtained film.
  • the obtained film was dried at 70 ° C. for 9 minutes to obtain a polarizing element having a thickness of 13 ⁇ m.
  • an alkali-treated triacetyl cellulose film (TD-80U manufactured by Fuji Photo Film Co., Ltd.) was used for the obtained polarizing element using a polyvinyl alcohol adhesive (NH-26 4 wt% aqueous solution manufactured by Nihon Vinegar Bipoval Co.).
  • a polarizing plate was obtained by laminating.
  • the obtained polarizing plate was cut into 40 mm ⁇ 40 mm, and bonded to a 1 mm glass plate via an adhesive PTR-3000 (manufactured by Nippon Kayaku Co., Ltd.) to obtain a measurement sample.
  • Example 2 The swollen film was mixed with 1500 parts by weight of water, 1.5 parts by weight of sodium tripolyphosphate, 1.5 parts by weight of anhydrous sodium sulfate, 0.038 parts by weight of dye (1), 0.16 parts by weight of dye (3), dye ( 4) The same method as in Example 1 except that 0.105 parts by weight of the dye and (5) 0.13 parts by weight of the dye were incorporated by immersion in an aqueous solution at 45 ° C. for 3 minutes 00 seconds. A measurement sample was prepared.
  • Example 3 The swollen film was mixed with 1500 parts by weight of water, 1.5 parts by weight of sodium tripolyphosphate, 1.5 parts by weight of anhydrous sodium sulfate, 0.038 parts by weight of dye (1), 0.17 parts by weight of dye (2), dye ( 3) 0.16 parts by weight, dye (4) 0.105 parts by weight and dye (5) 0.13 parts by weight were mixed in an aqueous solution at 45 ° C. for 4 minutes and 00 seconds to contain the dye. Except for the above, a measurement sample was prepared in the same manner as in Example 1.
  • Example 4 The swelled film was mixed with 1500 parts by weight of water, 1.5 parts by weight of sodium tripolyphosphate, 1.5 parts by weight of anhydrous sodium sulfate, 0.023 parts by weight of dye (1), 0.13 parts by weight of dye (2), dye ( 3) 0.16 parts by weight, dye (4) 0.12 parts by weight and dye (5) 0.10 parts by weight were mixed in an aqueous solution at 45 ° C. for 3 minutes 00 seconds to contain the dye. Except for the above, a measurement sample was prepared in the same manner as in Example 1.
  • Examples 5 to 14 Instead of a polyvinyl alcohol film having an average polymerization degree of 2400 (VF-PS manufactured by Kuraray Co., Ltd.) as a film to which the swelling process is applied, a polyvinyl alcohol film having an average polymerization 4000 (VF-XH # 7500 manufactured by Kuraray Co., Ltd.) is used.
  • VF-PS manufactured by Kuraray Co., Ltd.
  • VF-XH # 7500 manufactured by Kuraray Co., Ltd. VF-XH # 7500 manufactured by Kuraray Co., Ltd.
  • Example 3-1 to Example 3-14 In the dyeing process of Example 3, a measurement sample was produced in the same manner as in Example 1 except that a polarizing element having a different transmittance was produced by arbitrarily adjusting the time during which the swelled film was immersed in the dyeing solution. .
  • Comparative Example 1 A measurement sample was obtained in the same manner as in Example 1 except that an iodine-based polarizing element containing no azo compound was prepared according to the method of Comparative Example 1 of JP-A-2008-065222.
  • the polarizing element 2 contains an azo compound, but the polarizing element alone and two polarizing elements are arranged so that the absorption axis directions thereof are parallel to each other.
  • a dye-based polarizing element in which the absolute values of the chromaticity a * value and b * value obtained when measuring the transmittance of natural light are not optimized in a state where the sheets are arranged so that the absorption axis directions thereof are parallel to each other
  • a measurement sample was obtained in the same manner as in Example 1 except that the sample was prepared.
  • Example 3 Although containing an azo compound according to the method of Example 3 described in Japanese Patent No. 4162334, the polarizing element alone and the two polarizing elements are arranged so that the absorption axis directions thereof are parallel to each other, and the two polarizing elements A dye-type polarizing element in which the absolute values of the chromaticity a * value and b * value required at the time of measuring the transmittance of natural light are not optimized in a state where the absorption axes are arranged in parallel with each other A measurement sample was obtained in the same manner as in Example 1 except that.
  • Comparative Example 4 A measurement sample was obtained in the same manner as in Comparative Example 2 except that a polarizing plate having a single transmittance Ys of about 50% was produced by changing the dyeing time.
  • Example 5 A supercontrast polarizing plate SHC-125 manufactured by Polatechno Co., which generally exhibits a neutral color, was obtained, and a measurement sample was prepared in the same manner as in Example 1.
  • Example 6 A commonly used paper white polarizing plate SHC manufactured by Polatechno Co., Ltd., characterized in that the color obtained by measuring two polarizing elements in a state where their absorption axis directions are parallel to each other is white -115 was obtained, and the same method as in Example 1 was produced.
  • Evaluation 1 The following measurements and evaluations were performed on the measurement samples obtained in Examples 1 to 14 and Comparative Examples 1 to 6. Note that it has been confirmed in advance that the measurement sample has substantially the same evaluation result as that of the polarizing element before lamination (the same applies to evaluations 2 to 4).
  • Transmissivity Ts, Tp and Tc With respect to each measurement sample, transmittances Ts, Tp and Tc at each wavelength were measured using a spectrophotometer (“U-4100” manufactured by Hitachi, Ltd.).
  • the transmittance Ts is a spectral transmittance of each wavelength when a single measurement sample is measured.
  • the transmittance Tp is the spectral transmittance of each wavelength when two measurement samples are overlapped and measured so that their absorption axis directions are parallel
  • the transmittance Tc is the two measurement samples. It is the spectral transmittance of each wavelength when measured by overlapping the absorption axis directions so as to be orthogonal.
  • Single transmittance Ys, parallel transmittance Yp, and orthogonal transmittance Yc For each measurement sample, single transmittance Ys, parallel transmittance Yp, and orthogonal transmittance Yc were determined.
  • the single transmittance Ys, the parallel transmittance Yp, and the orthogonal transmittance Yc are the transmittances Ts, Tp, and Tc obtained at predetermined wavelength intervals d ⁇ (here, 10 nm) in the wavelength region of 400 to 700 nm.
  • d ⁇ here, 10 nm
  • the transmittances Ts, Tp and Tc were calculated by substituting them into the following formulas (V) to (VII).
  • P ⁇ represents the spectral distribution of the standard light (C light source)
  • y ⁇ represents the color matching function of the double field of view.
  • Table 1 The results for the single transmittance Ys are shown in Table 1.
  • a * -s and b * -s, a * -p and b * -p, and a * -c and b * -c are transmittance Ts, parallel transmittance Tp and orthogonal transmission. This corresponds to the chromaticity a * value and b * value in the measurement of the rate Tc, respectively.
  • the parallel color means a color when two identical samples are stacked so that their absorption axis directions are parallel to each other (in white display), and is the same as the parallel color. It means the color when two samples are stacked so that their absorption axis directions are orthogonal to each other (when black is displayed).
  • the polarization color is “white” for the parallel color and “black” for the orthogonal color. In this embodiment, for example, yellowish white is “yellow” or “yellowish green”. "Purple black is shown as” purple ".
  • the polarizing element according to the present invention is made of a base material containing an azo compound as a constituent component, has a single transmittance of 35% to 80%, and is a natural light source according to JIS Z 8781-4: 2013.
  • the absolute value of the chromaticity a * value and b * value obtained at the time of measuring the transmittance is 1 or less for each polarization element, and two polarization elements are arranged so that their absorption axis directions are parallel to each other
  • both were 2 or less in the state where the two polarizing elements were arranged so that the absorption axis directions thereof were orthogonal to each other.
  • achromatic white and achromatic black can be expressed in white display (parallel position) and black display (orthogonal position), respectively.
  • the transmittance Ky was measured so that the vibration direction of the absolute polarized light and the absorption axis direction of the measurement sample were orthogonal to each other (the absorption axis direction of the absolute polarizing plate and the absorption axis direction of the measurement sample were parallel).
  • the spectral transmittance of each wavelength at the time hereinafter referred to as “absolute parallel transmittance Ky”.
  • the transmittance Kz is measured when the vibration direction of the absolute polarized light and the absorption axis direction of the measurement sample are parallel (the absorption axis direction of the absolute polarizing plate and the absorption axis direction of the measurement sample are orthogonal).
  • the spectral transmittance of each wavelength hereinafter referred to as “absolute orthogonal transmittance Kz”.
  • the polarizing element according to the present invention has a transmittance of each wavelength measured by irradiating absolute polarized light so that the vibration direction of light is orthogonal to the absorption axis direction.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 4% or less, and the average of 600 nm to 670 nm
  • the absolute value of the difference between the transmittance and the average transmittance between 550 nm and 600 nm is 3% or less, and measured by irradiating with absolute polarized light so that the vibration direction of light is parallel to the absorption axis direction.
  • the absolute value of the difference between the average transmittance of 550 nm to 600 nm and the average transmittance of 400 nm to 460 nm is 2% or less. Te, and it was confirmed that the absolute value of the difference between the average transmittance and 550nm to 600nm average transmittance of 600nm to 670nm is adjusted to 2 or less.
  • the minimum polarization degree ⁇ y min1 or the minimum polarization degree ⁇ y min2 was determined for each measurement sample obtained in Examples 1 to 14 and Examples 3-1 to 3-14.
  • the minimum polarization degree ⁇ y min1 was obtained for each measurement sample having the single transmittance Ys of 35% to 60%, and was calculated by substituting the single transmittance Ys into the following formula (I).
  • the minimum polarization degree ⁇ y min2 was obtained for each measurement sample having the single transmittance Ys of more than 60% and 80% or less, and was calculated by substituting the single transmittance Ys into the following formula (II).
  • Table 3 the unit transmittance Ys and the degree of polarization ⁇ y of Examples 1 to 14 are the same as those shown in Table 1.
  • Ys is a single transmittance after the visibility correction.
  • the polarizing element according to the present invention has the minimum polarization degree ⁇ y min1 or the minimum polarization degree ⁇ y min2 calculated from the formula (I) or the formula (II) with respect to the single transmittance Ys. Was confirmed to have a high degree of polarization ⁇ y.
  • Such a polarizing plate of the present invention has high durability not obtained with an iodine-based polarizing plate, and even after applying a durability test, achromatic white when displaying white and achromatic when displaying black It was confirmed that a black color can be expressed.
  • the polarizing element of the present invention or the polarizing plate using the same not only high brightness and high contrast, but also high reliability, long-term high contrast, and high color reproducibility A device can be realized.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention concerne un élément de polarisation qui peut produire un blanc achromatique pendant l'affichage de blanc et un noir achromatique en affichage noir tout en ayant une transmittance élevée. L'élément de polarisation est formé d'un matériau de base contenant un composé azoïque en tant que composant constituant et est caractérisée en ce que la transmittance unitaire est de 35 à 80 % et par les valeurs absolues pour la valeur a* et la valeur b* de chromaticité selon JIS Z 8781-4:2013 pendant les mesures de transmittance pour une lumière naturelle étant de 1 ou moins dans un élément de lumière polarisée individuelle, 2 ou moins dans un état dans lequel deux éléments de polarisation sont disposés de sorte que les directions des axes d'absorption pour ceux-ci soient mutuellement parallèles, et 2 ou moins dans un état dans lequel deux éléments de polarisation sont disposés de sorte que les directions des axes d'absorption pour ceux-ci soient mutuellement orthogonaux.
PCT/JP2015/075017 2014-09-03 2015-09-02 Élément de polarisation, plaque de polarisation ayant ledit élément de polarisation, et dispositif d'affichage à cristaux liquides ayant ledit élément de polarisation ou ladite plaque de polarisation Ceased WO2016035838A1 (fr)

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JP2017090903A (ja) * 2015-11-06 2017-05-25 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液晶表示装置
WO2018079651A1 (fr) * 2016-10-31 2018-05-03 日本化薬株式会社 Élément de polarisation, plaque de polarisation utilisant celui-ci et dispositif d'affichage à cristaux liquides

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JPH05295281A (ja) * 1991-12-26 1993-11-09 Mitsui Toatsu Chem Inc 水溶性アゾ染料及び該染料を用いた偏光フィルム
WO2010095447A1 (fr) * 2009-02-20 2010-08-26 日本化薬株式会社 Plaque de polarisation contenant un colorant avec couche de résine durcie
WO2012165223A1 (fr) * 2011-05-30 2012-12-06 日本化薬株式会社 Plaque et élément de polarisation à base de colorant
JP2013057909A (ja) * 2011-09-09 2013-03-28 Nippon Kayaku Co Ltd 偏光素子、および、偏光板
WO2013141236A1 (fr) * 2012-03-19 2013-09-26 日本化薬株式会社 Polariseur à base de colorant et plaque polarisante
JP2013210624A (ja) * 2012-02-28 2013-10-10 Sumitomo Chemical Co Ltd 偏光膜、円偏光板及びそれらの製造方法
WO2015111472A1 (fr) * 2014-01-23 2015-07-30 日本化薬株式会社 Dispositif d'affichage doté d'un matériau de base ayant une fonction de polarisation

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JPH05295281A (ja) * 1991-12-26 1993-11-09 Mitsui Toatsu Chem Inc 水溶性アゾ染料及び該染料を用いた偏光フィルム
WO2010095447A1 (fr) * 2009-02-20 2010-08-26 日本化薬株式会社 Plaque de polarisation contenant un colorant avec couche de résine durcie
WO2012165223A1 (fr) * 2011-05-30 2012-12-06 日本化薬株式会社 Plaque et élément de polarisation à base de colorant
JP2013057909A (ja) * 2011-09-09 2013-03-28 Nippon Kayaku Co Ltd 偏光素子、および、偏光板
JP2013210624A (ja) * 2012-02-28 2013-10-10 Sumitomo Chemical Co Ltd 偏光膜、円偏光板及びそれらの製造方法
WO2013141236A1 (fr) * 2012-03-19 2013-09-26 日本化薬株式会社 Polariseur à base de colorant et plaque polarisante
WO2015111472A1 (fr) * 2014-01-23 2015-07-30 日本化薬株式会社 Dispositif d'affichage doté d'un matériau de base ayant une fonction de polarisation

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Publication number Priority date Publication date Assignee Title
JP2017090903A (ja) * 2015-11-06 2017-05-25 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液晶表示装置
WO2018079651A1 (fr) * 2016-10-31 2018-05-03 日本化薬株式会社 Élément de polarisation, plaque de polarisation utilisant celui-ci et dispositif d'affichage à cristaux liquides
JPWO2018079651A1 (ja) * 2016-10-31 2019-09-19 日本化薬株式会社 偏光素子、並びにこれを用いた偏光板及び液晶表示装置

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