Dye-based polarizing film, and polarizing plate and display device using the same

Abstract

A polarizing film, characterized in that it comprises a substrate, and the substrate contains an azo compound or a salt thereof (compound A) represented by formula (1) and an azo compound or a salt thereof (compound B) represented by formula (2), wherein in formula (1), X 1 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 1 and R 1 To R 4 Let X represent any substituent independently, and m represent an integer from 1 to 3. In equation (2), X 2 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 2 and R 5 To R 8 Each can independently represent any substituent, R 9 This represents a hydrogen atom or a methyl group, and n represents an integer from 1 to 3.

Description

Technical Field

[0001] This invention relates to a dye-based polarizing film with high polarization, high contrast and high durability, as well as a polarizing plate and display device using the same. Background Technology

[0002] A polarizing plate, which allows light to pass through and block it, together with a liquid crystal, which switches light, are the basic components of display devices such as Liquid Crystal Displays (LCDs). The applications of LCDs have expanded from early small machines such as calculators and clocks to include laptops, word processors, LCD projectors, LCD TVs, car navigation systems, and indoor and outdoor measuring instruments. Furthermore, they can be used in lenses with polarizing functions, resulting in sunglasses with improved visual clarity, and more recently, polarized glasses for 3D TVs. Because the applications of such polarizing plates have expanded to a wide range, they can be used under a wide range of conditions, from low to high temperatures, low to high humidity, and low to high light intensity, thus requiring polarizing plates with high polarization performance and high durability.

[0003] Currently, polarizing plates are manufactured by dyeing or impregnating films with iodine or dichroic dyes, or by stretching and oriented films impregnated with polyvinyl alcohol or its derivatives. Alternatively, they are manufactured by dehydrating polyvinyl chloride films with hydrochloric acid or polyvinyl alcohol-based films to generate polyenes and then oriented. Generally, iodine-based polarizing films using iodine exhibit excellent polarization performance, but they are not resistant to water and heat. Under prolonged use in high-temperature and high-humidity conditions, their durability can sometimes be compromised. To improve durability, methods such as treatment with formalin or aqueous solutions containing boric acid, or using low-permeability polymer films as protective films, have been considered, but their effectiveness is not entirely satisfactory.

[0004] Dye-based polarizing films using dichroic dyes employ a variety of colors of dye to cover a wide range of absorption bands, thereby creating polarizing films suitable for various purposes. For example, mixing any dye from yellow to orange, red to violet, and blue to green can yield polarizing films that cover the entire visible wavelength range for both transmission and absorption. On the other hand, compared to iodine, dye-based polarizing films exhibit superior heat and humidity resistance, as well as better lightfastness, but their optical properties are inferior.

[0005] In recent years, LED backlighting using LEDs has become mainstream in display devices, and its photometric and colorimetric properties are defined in JIS Z8724:2015. In this standard, the wavelength range for isochromatic functions is defined as 360nm to 830nm. When performing spectroscopic measurements of LED light sources for colorimetric purposes, the wavelength range can also be defined as 380nm to 780nm. From this, it is clear that in applications such as display devices using LED backlighting, the polarizing plates used must exhibit high optical characteristics at least up to 780nm in the wavelength range.

[0006] The mixing of common dichroic dyes, as illustrated in patent documents 1 to 5, 8 and 9, has gradually led to the development of dye-based polarizing plates with various characteristics. However, among the patents reported to date concerning polarizing plates for display devices, most only specify a wavelength range of 400 nm to 700 nm for optical measurement, or do not specify the wavelength range itself. Therefore, optical properties above 700 nm have hardly been discussed.

[0007] In the dye-based polarizing plate actually described in Patent Document 2, due to the low absorption performance above 700nm, a phenomenon of backlight leakage (hereinafter referred to as light leakage) occurs when the absorption axes of the two polarizing plates are orthogonally arranged.

[0008] On the other hand, as described in Patent Documents 10 and 11, there are also applications related to dye-based polarizing plates that specify a wavelength range of 380 nm to 780 nm for optical measurements. However, there is a need to improve the polarization performance in the visible light wavelength region of 380 nm to 780 nm.

[0009] In Example 13 of Patent Document 3, a combination of "diazo to triazo compound" or "diazo to triazo copper compound" is described. However, since the dye itself has low polarization performance, it cannot reach a level that satisfies the performance requirements for a polarizing film.

[0010] Tetraazo compounds and tetraazo copper dyes have been under development in recent years. Patent documents 1 to 8 describe dichroic pigments with good polarization properties and examples of formulations using them. For example, Example 8 of Patent Document 1 discloses a formulation containing a tetraazo compound and a tetraazo copper dye. However, the described contrast is low, and it has not been reported that the combination of a tetraazo compound and a tetraazo copper dye can achieve sufficient polarization performance in the 380 to 780 nm range.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: International Publication No. 2017 / 135392

[0014] Patent Document 2: International Publication No. 2016 / 186183

[0015] Patent Document 3: Japanese Patent Application Publication No. 2021-002043

[0016] Patent Document 4: Japanese Patent Application Publication No. 2017-090903

[0017] Patent Document 5: International Publication No. 2020 / 050333

[0018] Patent Document 6: International Publication No. 2012 / 108169

[0019] Patent Document 7: International Publication No. 2012 / 108173

[0020] Patent Document 8: International Publication No. 2017 / 135391

[0021] Patent Document 9: International Publication No. 2019 / 117131

[0022] Patent Document 10: International Publication No. 2022 / 071201

[0023] Patent Document 11: International Publication No. 2022 / 071204 Summary of the Invention

[0024] The problem the invention aims to solve

[0025] One object of the present invention is to provide a polarizing film with excellent (low) cross-transmittance at a wavelength of 730 nm, and polarizing plates and display devices (polarizing films, etc.) using the same. Another object of the present invention is to provide high-performance polarizing films with high polarization, high contrast, and high durability, particularly polarizing films with good contrast even in the visible light region, specifically the wavelength region of 380 to 780 nm, and in the wavelength region of 400 to 700 nm. Furthermore, another object of the present invention is to provide polarizing films with low light leakage at cross-positions. Additionally, another object of the present invention is to provide high-performance polarizing films with excellent polarization performance and durability, exhibiting improved durability under harsh environments (e.g., heat resistance, humidity resistance, light resistance, etc.).

[0026] Solution for solving the problem

[0027] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by mixing two azo compounds with specific structures, namely a tetraazo compound and a tetraazo copper compound, as dichroic dyes, it is possible to obtain a polarizing film with less light leakage at orthogonal positions above 700 nm, improved polarization performance, especially improved polarization degree and contrast, and high durability such as heat resistance, damp heat resistance, and light resistance, as well as a polarizing plate and display device using it, thereby completing the present invention.

[0028] That is, the present invention relates to the following [1] to [7], but is not limited thereto. [1]

[0030] A polarizing film, characterized in that it comprises a substrate, wherein the substrate contains an azo compound or a salt thereof (compound A) represented by formula (1) and an azo compound or a salt thereof (compound B) represented by formula (2).

[0031]

[0032] In equation (1), X 1 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 1 and R 1 To R 4 Each can independently represent any substituent, and m represents an integer from 1 to 3.

[0033]

[0034] In equation (2), X 2 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 2 and R 5 To R 8 Each can independently represent any substituent, R 9 This represents a hydrogen atom or a methyl group, and n represents an integer from 1 to 3. [2]

[0036] According to the polarizing film described in [1], wherein, in formula (1), R 1 To R 4 Each of these can be independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group containing a sulfonyl group.

[0037] X 1It is an unsubstituted amino group or having one or two C1-C4 alkyl or phenyl-substituted C1-C4 alkyl groups, or an unsubstituted amino group or having one or two substituents independently selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation and amino, of the form phenylamino, naphthylamino, benzoylamino, or naphthotriazolyl.

[0038] Q 1 It can be a hydrogen atom, a chlorine atom, a hydroxyl group, a hydroxyl group with a protecting group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy group with a sulfonyl group, a nitro group, a carboxyl group, or a sulfonyl group.

[0039] In equation (2), R 5 To R 8 Each of these can be independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group containing a sulfonyl group.

[0040] X 2 It is an unsubstituted amino group or having one or two C1-C4 alkyl or phenyl-substituted C1-C4 alkyl groups, or an unsubstituted amino group or having one or two substituents independently selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation and amino, of the form phenylamino, naphthylamino, benzoylamino, or naphthotriazolyl.

[0041] Q 2 It can be a hydrogen atom, a chlorine atom, a hydroxyl group, a hydroxyl group with a protecting group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy group with a sulfonyl group, a nitro group, a carboxyl group, or a sulfonyl group. [3]

[0043] According to the polarizing film described in [1], the azo compound or its salt represented by the above formula (1) is an azo compound or its salt represented by the following formula (3), and the azo compound or its salt represented by the above formula (2) is an azo compound or its salt represented by the following formula (4).

[0044]

[0045] In equation (3), R 1 To R 4 Each of these can independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group with a sulfonyl group, where m represents an integer from 1 to 3.

[0046]

[0047] In equation (4), R 5 To R 8Each of the following independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group with a sulfonyl group, R 9 denoted by methyl, and n represents an integer from 1 to 3.

[0048] [4] The polarizing film according to [1] contains one or more dichroic dyes other than compounds A and B.

[0049] [5] The polarizing film according to [1], wherein the substrate contains a polyvinyl alcohol-based resin.

[0050] [6] A polarizing plate having a transparent protective film disposed on one or both sides of the polarizing film described in any one of [1] to [5].

[0051] [7] A display device comprising the polarizing plate described in [6].

[0052] The effects of the invention

[0053] According to the present invention, a polarizing film having excellent orthogonal transmittance at a wavelength of 730 nm can be provided. In another aspect, a polarizing film having excellent polarization and contrast in the visible light region and in the wavelength regions of 380 to 780 nm and 400 to 700 nm can be provided. Detailed Implementation

[0054] In this specification and claims, unless explicitly stated in the case of free form, "azo compound or salt thereof" is sometimes simply referred to as "azo compound".

[0055] In this specification and claims, the term "substituent" may include a hydrogen atom; therefore, for convenience, a hydrogen atom is sometimes referred to as a "substituent." "Optionally having substituents" also includes cases without substituents. For example, "optionally having substituents" includes both unsubstituted, plain phenyl and substituted phenyl.

[0056] The polarizing film of the present invention is characterized in that it contains a substrate, and the substrate contains an azo compound or a salt thereof (compound A) represented by the following formula (1) and an azo compound or a salt thereof (compound B) represented by the following formula (2).

[0057]

[0058] In equation (1), X 1 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 1 and R 1 To R4 Each can independently represent any substituent, and m represents an integer from 1 to 3.

[0059]

[0060] In equation (1), X 2 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 2 and R 5 To R 8 Each can independently represent any substituent, R 9 This represents a hydrogen atom or a methyl group, and n represents an integer from 1 to 3.

[0061] In formulas (1) and (2), the ring structures depicted by the solid and dashed lines represent phenyl (phenylene) or naphthyl (naphthylene).

[0062] In equations (1) and (2) above, X 1 With X 2 Each of the following groups independently represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, and a naphthotriazolyl group optionally having a substituent, Q. 1 With Q 2 and R 1 To R 8 Each can independently represent any substituent. As the aforementioned optional substituents, and Q... 1 With Q 2 and R 1 To R 8 Any substituents shown may include, for example: diazonyl, heterocyclic amino, fused-ring heterocyclic amino, alkyl, alkoxy, alkoxy with sulfonyl, aryloxy, alkyl carbonylamino, aryl carbonylamino, alkyl carbonyloxy, aryl carbonyloxy, alkyl carbonyl, aryl carbonyl, alkyl carbamoyl, aryl carbamoyl, alkoxy carbonyl, aryloxy carbonyl, alkyl sulfonylamino, aryl sulfonylamino, alkyl aminosulfonyl, aryl aminosulfonyl, alkyl sulfonyl, aryl sulfonyl, alkyl thio, aryl thio, alkyl urea, aryl urea, alkoxy carbonylamino, aryloxy carbonylamino, alkylamino, arylamino, hydroxyl (-OH), hydroxyl with protecting group (-OP), cyano (-CN), nitro (-NO2), mercapto (-SH), halogen atom, carboxyl (-CO2H), sulfonyl (-SO3H), amino (-NH2), hydrogen atom, etc.

[0063] Examples of heterocyclic amino groups include 5- or 6-membered rings comprising 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms. Specific examples of such heterocyclic amino groups include:

[0064] Five-membered heterocyclic amino groups, such as pyrrolidinylamino, tetrahydrofuranylamino, tetrahydrothiophene-2-ylamino, and tetrahydrothiophene-3-ylamino;

[0065] Six-membered heterocyclic amino groups, including piperidinylamino, piperazinylamino, dioxane-2-ylamino, morpholinylamino, and thiomorpholinylamino;

[0066] Pyrroleamino, pyrazoleamino, imidazoleamino, triazoleamino, furanylamino, thiophene-2-ylamino, thiophene-3-ylamino, oxazolamino, thiazoleamino, and other five-membered aromatic heterocyclic amino groups; or

[0067] Six-membered aromatic heterocyclic amino groups, such as pyridylamino, pyrazinylamino, pyridazinylamino, and triazinylamino; etc.

[0068] The heterocyclic group described above preferably has an aromatic ring as its heterocyclic portion. Furthermore, the heteroatoms constituting the heterocycle are preferably selected from nitrogen and sulfur atoms.

[0069] Examples of fused-ring heterocyclic amino groups include those with a benzene ring fused to a 5- or 6-membered heterocyclic group comprising 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms. Specific examples of such fused-ring heterocyclic amino groups include:

[0070] Phthalimide and other heterocyclic moieties are 5-membered alicyclic fused-ring heterocyclic amino groups;

[0071] The heterocyclic moiety of benzopyranylamino and other heterocyclic amino groups is a 6-membered alicyclic fused-ring heterocyclic amino group;

[0072] Benzopyrroleamino, benzopyrazoleamino, benzimizazoleamino, benzotriazoleamino, benzofuranylamino, benzothiophene-2-ylamino, benzothiophene-3-ylamino, benzoxazoleamino, benzothiazoleamino, etc., are fused-ring aromatic heterocyclic amino groups with an aromatic five-membered ring as the heterocyclic part; or

[0073] Quinolinylamino, borynylamino, phthalazinylamino, quinazolinylamino, quinoxalinylamino, and quinoxalinylamino are fused-ring aromatic heterocyclic amino groups whose heterocyclic part is an aromatic six-membered ring.

[0074] The heterocyclic group described above preferably has an aromatic ring as its heterocyclic portion. Furthermore, the heteroatoms constituting the heterocycle are preferably selected from nitrogen and sulfur atoms.

[0075] Examples of alkyl groups include straight-chain, branched, or cyclic alkyl groups, with C1-C2 being the most preferred. 10 Alkyl group. As a C1-C 10 Specific examples of alkyl groups can be listed, for example:

[0076] Straight-chain C1-C groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. 10 alkyl;

[0077] Isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, tert-hexyl, isoheptyl, tert-heptyl, isooctyl, tert-octyl, 2-ethylhexyl, isononyl, isodecyl, and other branched C3-C compounds. 10 Alkyl; or

[0078] Cyclic C3-C7 alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl are preferred. Among them, straight-chain or branched alkyl groups are preferred, and straight-chain C1-C4 alkyl groups are more preferred.

[0079] Examples of alkoxy groups include straight-chain, branched, or cyclic alkoxy groups, with C1-C2 being the most preferred. 10 Alkyl groups. As C1-C 10 Specific examples of alkoxy groups can be listed as follows:

[0080] Methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, and other straight-chain C1-C compounds. 10 Alkoxy;

[0081] Isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, isopentoxy, tert-pentoxy, isohexoxy, tert-hexoxy, isoheptoxy, tert-heptoxy, isooctoxy, tert-octoxy, 2-ethylhexoxy, isononoxy, isodecanoxy, and other branched C3-C compounds. 10 alkoxy; or

[0082] Cyclic C3-C7 alkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and cycloheptoxy are preferred. Among them, straight-chain or branched alkoxy groups are preferred, and straight-chain C1-C4 alkoxy groups are more preferred.

[0083] As the above-mentioned alkoxy group having a sulfonyl group,

[0084] Preferably, a C1-C4 straight-chain alkoxy group is used as the substitution position for the sulfonyl group, with the alkoxy terminus being preferred. More preferably, 3-sulfopropoxy and 4-sulfobutoxy are used, with 3-sulfopropoxy being particularly preferred.

[0085] The aryloxy group is preferably C6-C. 12Aryloxy groups, as specific examples, include phenoxy, naphthoxy, biphenyloxy, etc.

[0086] Examples of alkyl carbonyl amino groups include straight-chain, branched, or cyclic alkyl carbonyl amino groups, with C1-C2 being the most preferred. 10 Alkyl carbonyl amino. As C1-C 10 Specific examples of alkyl carbonyl amino groups can be listed as follows:

[0087] Methylcarbonylamino (acetylamino), ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n-pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n-nonylcarbonylamino, n-decylcarbonylamino, etc., are straight-chain C1-C... 10 Alkyl carbonyl amino;

[0088] Isopropylcarbonylamino, isobutylcarbonylamino, sec-butylcarbonylamino, tert-butylcarbonylamino, isopentylcarbonylamino, tert-pentylcarbonylamino, isohexylcarbonylamino, tert-hexylcarbonylamino, isoheptylcarbonylamino, tert-heptylcarbonylamino, isooctylcarbonylamino, tert-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino, and other branched C3-C... 10 alkylcarbonylamino; or

[0089] Cyclic C3-C7 alkyl carbonylamino groups, such as cyclopropyl carbonylamino, cyclobutyl carbonylamino, cyclopentyl carbonylamino, cyclohexyl carbonylamino, and cycloheptyl carbonylamino, are preferred. Among these, straight-chain or branched alkyl carbonylamino groups are preferred, and straight-chain alkyl carbonylamino groups are more preferred.

[0090] The above-mentioned aryl carbonyl amino group is preferably C6-C. 12 Aryl carbonyl amino groups, as specific examples, include phenyl carbonyl amino (benzoyl amino), naphthyl carbonyl amino, biphenyl carbonyl amino, etc.

[0091] Examples of alkyl carbonyloxy groups include straight-chain, branched, or cyclic alkyl carbonyloxy groups, with C1-C2 being the most preferred. 10 Alkyl carbonyloxy group. As a C1-C 10 Specific examples of alkyl carbonyloxy groups can be listed as follows:

[0092] Straight-chain C1-C atoms such as methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, n-butyl carbonyloxy, n-pentyl carbonyloxy, n-hexyl carbonyloxy, n-heptyl carbonyloxy, n-octyl carbonyloxy, n-nonyl carbonyloxy, and n-decyl carbonyloxy 10 alkylcarbonyloxy;

[0093] Isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, isopentylcarbonyloxy, tert-pentylcarbonyloxy, isohexylcarbonyloxy, tert-hexylcarbonyloxy, isoheptylcarbonyloxy, tert-heptylcarbonyloxy, isooctylcarbonyloxy, tert-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy, and other branched C3-C... 10 alkylcarbonyloxy; or

[0094] Cyclic C3-C7 alkyl carbonyloxy groups, such as cyclopropyl carbonyloxy, cyclobutyl carbonyloxy, cyclopentyl carbonyloxy, cyclohexyl carbonyloxy, and cycloheptyl carbonyloxy. Among these, straight-chain or branched alkyl carbonyloxy groups are preferred, and straight-chain alkyl carbonyloxy groups are more preferred.

[0095] The above-mentioned aryl carbonyloxy group is preferably C6-C. 12 Aryl carbonyloxy groups, as specific examples, include phenyl carbonyloxy, naphthyl carbonyloxy, biphenyl carbonyloxy, etc.

[0096] Examples of alkyl carbonyl groups include straight-chain, branched, or cyclic alkyl carbonyl groups, with C1-C2 being the most preferred. 10 Alkyl carbonyl group. As a C1-C... 10 Specific examples of alkyl carbonyl groups can be listed as follows:

[0097] Straight-chain C1-C groups include methyl carbonyl, ethyl carbonyl, n-propyl carbonyl, n-butyl carbonyl, n-pentyl carbonyl, n-hexyl carbonyl, n-heptyl carbonyl, n-octyl carbonyl, n-nonyl carbonyl, and n-decyl carbonyl. 10 Alkyl carbonyl;

[0098] Isopropyl carbonyl, isobutyl carbonyl, sec-butyl carbonyl, tert-butyl carbonyl, isopentyl carbonyl, tert-pentyl carbonyl, isohexyl carbonyl, tert-hexyl carbonyl, isohexyl carbonyl, tert-heptyl carbonyl, isooctyl carbonyl, tert-octyl carbonyl, 2-ethylhexyl carbonyl, isononyl carbonyl, isodecyl carbonyl, and other branched C3-C groups. 10 alkyl carbonyl; or

[0099] Cyclic C3-C7 alkyl carbonyl groups, such as cyclopropyl carbonyl, cyclobutyl carbonyl, cyclopentyl carbonyl, cyclohexyl carbonyl, and cycloheptyl carbonyl. Among them, straight-chain or branched alkyl carbonyl groups are preferred, and straight-chain alkyl carbonyl groups are more preferred.

[0100] As the above-mentioned aryl carbonyl group, C6-C is preferred. 12 Aryl carbonyl groups, as specific examples, include phenyl carbonyl (benzoyl), naphthyl carbonyl, biphenyl carbonyl, etc.

[0101] Examples of alkyl carbamoyl groups include linear, branched, or cyclic monoalkyl carbamoyl groups or dialkyl carbamoyl groups.

[0102] As a monoalkylcarbamoyl group, a monoC1-C group is preferred. 10 Alkyl carbamoyl, as specific examples, can be listed as follows:

[0103] Straight-chain mono-C1-C compounds such as methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, n-butylcarbamoyl, n-pentylcarbamoyl, n-hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, and n-decylcarbamoyl 10 Alkyl carbamoyl;

[0104] Isopropylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, tert-butylcarbamoyl, isopentylcarbamoyl, tert-pentylcarbamoyl, isohexylcarbamoyl, tert-hexylcarbamoyl, isoheptylcarbamoyl, tert-heptylcarbamoyl, isooctylcarbamoyl, tert-octylcarbamoyl, 2-ethylhexylcarbamoyl, isononylcarbamoyl, isodecylcarbamoyl, and other branched single C3-C compounds. 10 alkylcarbamoyl; or

[0105] Cyclic mono-C3-C7 alkyl carbamoyl groups, such as cyclopropylcarbamoyl, cyclobutylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, and cycloheptylcarbamoyl, are preferred. Among these, linear or branched monoalkyl carbamoyl groups are preferred, with linear monoalkyl carbamoyl groups being more preferable.

[0106] As a dialkylcarbamoyl group, a diC1-C2 group is preferred. 10 Alkyl carbamoyl, as specific examples, can be listed as follows:

[0107] Straight-chain di-C1-C compounds such as dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, di-n-butylcarbamoyl, di-n-pentylcarbamoyl, di-n-hexylcarbamoyl, di-n-heptylcarbamoyl, di-n-octylcarbamoyl, di-n-nonylcarbamoyl, and di-n-decylcarbamoyl 10 Alkyl carbamoyl;

[0108] Diisopropylcarbamoyl, diisobutylcarbamoyl, disec-butylcarbamoyl, ditert-butylcarbamoyl, diisopentylcarbamoyl, ditert-pentylcarbamoyl, diisohexylcarbamoyl, ditert-hexylcarbamoyl, diisoheptylcarbamoyl, ditert-heptylcarbamoyl, diisooctylcarbamoyl, ditert-octylcarbamoyl, di-(2-ethylhexyl)carbamoyl, diisononylcarbamoyl, diisodecylcarbamoyl, etc., are branched di-C3-C compounds with two branches. 10 alkylcarbamoyl; or

[0109] Bicyclopropylcarbamoyl, bicyclobutylcarbamoyl, bicyclopentylcarbamoyl, bicyclohexylcarbamoyl, bicycloheptylcarbamoyl, and other cyclic di-C3-C7 alkylcarbamoyl groups having two rings are preferred. Among them, straight-chain or branched dialkylcarbamoyl groups are preferred, and straight-chain dialkylcarbamoyl groups are more preferred.

[0110] Examples of aryl carbamoyl groups include monoaryl carbamoyl groups and diaryl carbamoyl groups.

[0111] The monoaryl carbamoyl group is preferably a mono-C6-C group. 12 Arylcarbamoyl, as specific examples, include phenylcarbamoyl, naphthylcarbamoyl, biphenylcarbamoyl, etc.

[0112] As a diarylcarbamoyl group, a diC6-C group is preferred. 12 Arylcarbamoyl, as specific examples, include diphenylcarbamoyl, dinaphthylcarbamoyl, di(biphenyl)carbamoyl, etc.

[0113] Examples of alkoxycarbonyl groups include straight-chain, branched, or cyclic alkoxycarbonyl groups, with C1-C2 being the most preferred. 10 Alkoxycarbonyl. As a C1-C 10 Specific examples of alkoxy carbonyl groups can be listed as follows:

[0114] Straight-chain C1-C groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexoxycarbonyl, heptoxycarbonyl, octoxycarbonyl, nonoxycarbonyl, and decoxycarbonyl 10 alkoxycarbonyl;

[0115] Branched C3-C groups include isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, isopentoxycarbonyl, tert-pentoxycarbonyl, isohexoxycarbonyl, tert-hexyloxycarbonyl, isohexyloxycarbonyl, tert-heptoxycarbonyl, isooctoxycarbonyl, tert-octoxycarbonyl, 2-ethylhexyloxycarbonyl, isononoxycarbonyl, and isodexoxycarbonyl. 10 alkoxycarbonyl; or

[0116] Cyclic C3-C7 alkoxycarbonyl groups, such as cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl, cyclohexyloxycarbonyl, and cycloheptoxycarbonyl. Among these, linear or branched alkoxycarbonyl groups are preferred, with linear alkoxycarbonyl groups being more preferred.

[0117] The aryloxycarbonyl group is preferably C6-C. 12Specific examples of aryloxycarbonyl groups include phenoxycarbonyl, naphthoxycarbonyl, and biphenyloxycarbonyl.

[0118] Examples of alkylsulfonylamino groups include linear, branched, or cyclic alkylsulfonylamino groups, with C1-C2 being the most preferred. 10 Alkylsulfonylamino. As a C1-C 10 Specific examples of alkylsulfonylamino groups can be listed as follows:

[0119] Straight-chain C1-C such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n-pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, n-decylsulfonylamino 10 alkylsulfonylamino;

[0120] Isopropylsulfonylamino, isobutylsulfonylamino, sec-butylsulfonylamino, tert-butylsulfonylamino, isopentylsulfonylamino, tert-pentylsulfonylamino, isohexylsulfonylamino, tert-hexylsulfonylamino, isoheptylsulfonylamino, tert-heptylsulfonylamino, isooctylsulfonylamino, tert-octylsulfonylamino, 2-ethylhexylsulfonylamino, isononylsulfonylamino, isodecylsulfonylamino, and other branched C3-C... 10 alkylsulfonylamino; or

[0121] Cyclic C3-C7 alkylsulfonylamino groups such as cyclopropylsulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, and cycloheptylsulfonylamino. Among them, linear or branched alkylsulfonylamino groups are preferred, and linear alkylsulfonylamino groups are more preferred.

[0122] The above-mentioned arylsulfonylamino group is preferably C6-C. 12 Arylsulfonylamino, as specific examples, include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino, etc.

[0123] Examples of alkylaminosulfonyl groups include linear, branched, or cyclic monoalkylaminosulfonyl groups or dialkylaminosulfonyl groups.

[0124] Monoalkylaminosulfonyl group is preferably monoC1-C 10 Alkylaminosulfonyl groups, as specific examples, can be listed as follows:

[0125] Straight-chain mono-C1-C aminosulfonyl, ethylaminosulfonyl, n-propylaminosulfonyl, n-butylaminosulfonyl, n-pentylaminosulfonyl, n-hexylaminosulfonyl, n-heptylaminosulfonyl, n-octylaminosulfonyl, n-nonylaminosulfonyl, n-decylaminosulfonyl, etc. 10Alkylaminosulfonyl;

[0126] Isopropylamine sulfonyl, isobutylamine sulfonyl, sec-butylamine sulfonyl, tert-butylamine sulfonyl, isopentylamine sulfonyl, tert-pentylamine sulfonyl, isohexylamine sulfonyl, tert-hexylamine sulfonyl, isoheptylamine sulfonyl, tert-heptylamine sulfonyl, isooctylamine sulfonyl, tert-octylamine sulfonyl, 2-ethylhexylamine sulfonyl, isononylamine sulfonyl, isodecylamine sulfonyl, and other branched single C3-C groups. 10 alkylaminosulfonyl; or

[0127] Cyclic mono-C3-C7 alkyl sulfonyl groups, such as cyclopropylaminosulfonyl, cyclobutylaminosulfonyl, cyclopentylaminosulfonyl, cyclohexylaminosulfonyl, and cycloheptylaminosulfonyl. Preferably, linear or branched monoalkyl sulfonyl groups are used, with linear monoalkyl sulfonyl groups being more preferred.

[0128] Dialkylaminosulfonyl group is preferably diC1-C 10 Alkylaminosulfonyl groups, as specific examples, can be listed as follows:

[0129] Straight-chain di-C1-C such as dimethylaminosulfonyl, diethylaminosulfonyl, di-n-propylaminosulfonyl, di-n-butylaminosulfonyl, di-n-pentylaminosulfonyl, di-n-hexylaminosulfonyl, di-n-heptylaminosulfonyl, di-n-octylaminosulfonyl, di-n-nonylaminosulfonyl, di-n-decylaminosulfonyl 10 Alkylaminosulfonyl;

[0130] Diisopropylaminosulfonyl, diisobutylaminosulfonyl, disec-butylaminosulfonyl, ditert-butylaminosulfonyl, diisopentylaminosulfonyl, ditert-pentylaminosulfonyl, diisohexylaminosulfonyl, ditert-hexylaminosulfonyl, diisoheptylaminosulfonyl, ditert-heptylaminosulfonyl, diisooctylaminosulfonyl, ditert-octylaminosulfonyl, di-(2-ethylhexyl)aminosulfonyl, diisononylaminosulfonyl, diisodecylaminosulfonyl, etc., are branched di-C3-C chains with two branches. 10 alkylaminosulfonyl; or

[0131] Cyclic di-C3-C7 alkyl sulfonyl groups having two rings include dicyclopropylaminosulfonyl, dicyclobutylaminosulfonyl, dicyclopentylaminosulfonyl, dicyclohexylaminosulfonyl, and dicycloheptylaminosulfonyl. Among these, linear or branched dialkyl sulfonyl groups are preferred, with linear dialkyl sulfonyl groups being more preferred.

[0132] Examples of aryl aminosulfonyl groups include monoaryl aminosulfonyl groups and diaryl aminosulfonyl groups.

[0133] Monoarylaminosulfonyl is preferably monoC6-C. 12Arylaminosulfonyl groups, as specific examples, include phenylaminosulfonyl, naphthylaminosulfonyl, biphenylaminosulfonyl, etc.

[0134] The diarylaminosulfonyl group is preferably diC6-C. 12 Arylaminosulfonyl groups, as specific examples, include diphenylaminosulfonyl, dinaphthylaminosulfonyl, di(biphenyl)aminosulfonyl, etc.

[0135] Examples of alkyl sulfonyl groups include linear, branched, or cyclic alkyl sulfonyl groups, with C1-C2 being the most preferred. 12 Alkyl sulfonyl group. As a C1-C 12 Specific examples of alkyl sulfonyl groups can be listed as follows:

[0136] Straight-chain C1-C such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, n-pentylsulfonyl, n-hexylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, n-nonylsulfonyl, n-decylsulfonyl, n-undecylsulfonyl, n-dodecylsulfonyl, etc. 12 alkylsulfonyl;

[0137] Isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, isopentylsulfonyl, tert-pentylsulfonyl, isohexylsulfonyl, tert-hexylsulfonyl, isoheptylsulfonyl, tert-heptylsulfonyl, isooctylsulfonyl, tert-octylsulfonyl, 2-ethylhexylsulfonyl, isononylsulfonyl, isodecylsulfonyl, isoundecylsulfonyl, tert-undecylsulfonyl, isododecylsulfonyl, tert-dodecylsulfonyl, and other branched C3-C groups 12 alkylsulfonyl; or

[0138] Cyclic C3-C7 alkylsulfonyl groups, such as cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, and cycloheptylsulfonyl. Among them, linear or branched alkylsulfonyl groups are preferred, and linear alkylsulfonyl groups are more preferred.

[0139] The above-mentioned aryl sulfonyl group is preferably C6-C. 12 Arylsulfonyl groups, as specific examples, include phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl, etc.

[0140] Examples of alkylthio groups include linear, branched, or cyclic alkylthio groups, with C1-C2 being the most preferred. 10 Alkylthio group. As a C1-C 10 Specific examples of alkylthio groups can be listed as follows:

[0141] Straight-chain C1-C groups such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, and n-decylthio.10 Alkylthio;

[0142] Isopropyl thio, isobutyl thio, sec-butyl thio, tert-butyl thio, isopentyl thio, tert-pentyl thio, isohexyl thio, tert-hexyl thio, isoheptyl thio, tert-heptyl thio, isooctyl thio, tert-octyl thio, 2-ethylhexyl thio, isononyl thio, isodecyl thio, and other branched C3-C groups 10 Alkylthio; or

[0143] Cyclic C3-C7 alkylthio groups such as cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, and cycloheptylthio. Among them, linear or branched alkylthio groups are preferred, and linear alkylthio groups are more preferred.

[0144] The above-mentioned arylthio group is preferably C6-C. 12 Aryl thiols, as specific examples, include phenylthiols, naphthiols, biphenylthiols, etc.

[0145] Examples of alkylurea groups include linear, branched, or cyclic monoalkylurea or dialkylurea groups.

[0146] As a monoalkylurea group, a monoC1-C group is preferred. 10 Alkyl urea groups, as specific examples, can be listed as follows:

[0147] Straight-chain mono-C1-C compounds such as methylurea, ethylurea, n-propylurea, n-butylurea, n-pentylurea, n-hexylurea, n-heptylurea, n-octylurea, n-nonylurea, and n-decylurea. 10 Alkyl urea;

[0148] Isopropylurea, isobutylurea, sec-butylurea, tert-butylurea, isopentylurea, tert-pentylurea, isohexylurea, tert-hexylurea, isoheptylurea, tert-heptylurea, isooctylurea, tert-octylurea, 2-ethylhexylurea, isononylurea, isodecylurea, etc., are branched single C3-C groups. 10 Alkyl urea; or

[0149] Cyclic mono-C3-C7 alkyl urea groups include cyclopropylurea, cyclobutylurea, cyclopentylurea, cyclohexylurea, and cycloheptylurea. Among these, linear or branched alkyl urea groups are preferred, with examples including linear alkyl urea groups.

[0150] Dialkylurea group is preferably diC1-C 10 Alkyl urea groups, as specific examples, can be listed as follows:

[0151] Straight-chain di-C1-C compounds such as dimethylurea, diethylurea, di-n-propylurea, di-n-butylurea, di-n-pentylurea, di-n-hexylurea, di-n-heptylurea, di-n-octylurea, di-n-nonylurea, and di-n-decylurea. 10 Alkyl urea;

[0152] Diisopropylurea, diisobutylurea, disec-butylurea, ditert-butylurea, diisopentylurea, ditert-pentylurea, diisohexylurea, ditert-hexylurea, diisoheptylurea, ditert-heptylurea, diisooctylurea, ditert-octylurea, di-(2-ethylhexyl)urea, diisononylurea, diisodecylurea, etc., are branched di-C3-C compounds with two branches. 10 Alkyl urea; or

[0153] Cyclic di-C3-C7 alkyl urea groups having two rings include dicyclopropylurea, dicyclobutylurea, dicyclopentylurea, dicyclohexylurea, and dicycloheptylurea. Among these, linear or branched dialkyl urea groups are preferred, with linear dialkyl urea groups being more preferred.

[0154] Examples of arylureido groups include monoarylureido groups and diarylureido groups.

[0155] As a monoaryl urea group, a mono-C6-C group is preferred. 12 Arylurea, as specific examples, include phenylurea, naphthylurea, biphenylurea, etc.

[0156] The diarylureid group is preferably diC6-C. 12 Arylurea, as specific examples, include diphenylurea, naphthylurea, and di(biphenyl)urea.

[0157] Examples of the above-mentioned alkoxycarbonyl amino groups include straight-chain, branched, or cyclic alkoxycarbonyl amino groups, with C1-C2 being the most preferred. 10 Alkoxycarbonylamino. As a C1-C 10 Specific examples of alkoxycarbonyl amino groups can be listed as follows:

[0158] Straight-chain C1-C amino groups such as methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonylamino, n-pentoxycarbonylamino, n-hexyloxycarbonylamino, n-heptoxycarbonylamino, n-octoxycarbonylamino, n-nonoxycarbonylamino, and n-decoxycarbonylamino 10 alkoxycarbonylamino;

[0159] Branched C3-C amino groups include isopropoxycarbonylamino, isobutoxycarbonylamino, sec-butoxycarbonylamino, tert-butoxycarbonylamino, isopentoxycarbonylamino, tert-pentoxycarbonylamino, isohexoxycarbonylamino, tert-hexoxycarbonylamino, isohexyloxycarbonylamino, tert-heptoxycarbonylamino, isooctoxycarbonylamino, tert-octoxycarbonylamino, 2-ethylhexoxycarbonylamino, isononoxycarbonylamino, and isodexoxycarbonylamino. 10 alkoxycarbonylamino; or

[0160] Cyclic C3-C7 alkoxycarbonylamino groups include cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, and cycloheptoxycarbonylamino. Among these, linear or branched alkoxycarbonylamino groups are preferred, with linear alkoxycarbonylamino groups being more preferred.

[0161] As the above-mentioned aryloxycarbonyl amino group, C6-C is preferred. 12 Aryloxycarbonylamino, as specific examples, include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, etc.

[0162] Examples of alkylamino groups include linear, branched, or cyclic monoalkylamino or dialkylamino groups.

[0163] Monoalkylamino is preferably monoC1-C 10 Alkylamino groups, as specific examples, can be listed as follows:

[0164] Straight-chain mono-C1-C amino groups such as methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, and n-decylamino 10 Alkylamino;

[0165] Isopropylamino, isobutylamino, sec-butylamino, tert-butylamino, isopentylamino, tert-pentylamino, isohexylamino, tert-hexylamino, isoheptylamino, tert-heptylamino, isooctylamino, tert-octylamino, 2-ethylhexylamino, isononylamino, isodecylamino, and other branched single C3-C amino groups. 10 alkylamino; or

[0166] Cyclic mono-C3-C7 alkylamino groups such as cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, and cycloheptylamino. Among them, linear or branched monoalkylamino groups are preferred, and linear monoalkylamino groups are more preferred.

[0167] Dialkylamino is preferably diC1-C 10 Alkylamino groups, as specific examples, can be listed as follows:

[0168] Straight-chain di-C1-C amino groups such as dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n-nonylamino, and di-n-decylamino. 10 Alkylamino;

[0169] Diisopropylamino, diisobutylamino, disec-butylamino, ditert-butylamino, diisopentylamino, ditert-pentylamino, diisohexylamino, ditert-hexylamino, diisoheptylamino, ditert-heptylamino, diisooctylamino, ditert-octylamino, di-(2-ethylhexyl)amino, diisononylamino, diisodecylamino, etc., are branched di-C3-C compounds with two branches. 10 alkylamino; or

[0170] Cyclic di-C3-C7 alkylamino groups having two rings, such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, and dicycloheptylamino. Among them, straight-chain or branched dialkylamino groups are preferred, and straight-chain dialkylamino groups are more preferred.

[0171] Examples of aryl amino groups include monoaryl amino groups and diaryl amino groups.

[0172] As a monoarylamino group, a mono-C6-C group is preferred. 12 Arylamino groups, as specific examples, include phenylamino (aniline), naphthylamino, biphenylamino, etc.

[0173] The diarylamino group is preferably diC6-C. 12 Arylamino groups, as specific examples, include diphenylamino, dinoxyamino, and di(biphenyl)amino.

[0174] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine, chlorine, or bromine atoms being preferred.

[0175] The above protecting groups are not particularly limited as long as they are groups commonly used as protecting groups for hydroxyl groups. Examples include: tert-butyldimethylsilyl (TBS), trimethylsilyl (TMS), methyl (Me) (forming a C1 alkoxy group together with the hydroxyl moiety), benzyl (Bn) (forming a phenyl-substituted C1 alkoxy group together with the hydroxyl moiety), p-methoxybenzyl (PMB) (forming a p-methoxyphenyl-substituted C1 alkoxy group together with the hydroxyl moiety), toluenesulfonyl (Ts), allyl, acetyl (Ac) (forming a C1 alkyl carbonyl group together with the hydroxyl moiety), triphenylmethyl (Tr) (forming a triphenyl-substituted C1 alkoxy group together with the hydroxyl moiety), and benzoyl (Bz) (forming a phenyl carbonyl group together with the alkoxy moiety).

[0176] As a more preferred R 1To R 8 Examples of such elements include: hydrogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, and C1-C4 alkoxy groups with sulfonyl groups.

[0177] Q is a better option 1 and Q 2 Examples of such elements include: hydrogen atom, chlorine atom, hydroxyl group, hydroxyl group with a protecting group, C1-C4 alkyl group, C1-C4 alkoxy group, C1-C4 alkoxy group with a sulfonyl group, nitro group, carboxyl group, and sulfonyl group.

[0178] As a more preferred X 1 and X 2 Examples include:

[0179] Amino groups that are unsubstituted or have one or two C1-C4 alkyl groups;

[0180] A phenylamino group that is unsubstituted or has one or two substituents selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation, and amino.

[0181] Naphthylamino is unsubstituted or has one or two substituents selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation, and amino.

[0182] Benzoylamino group without substitution or having one or two substituents selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation, and amino; or

[0183] Naphthotriazolyl is unsubstituted or has one or two substituents selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation, and amino.

[0184] The C1-C4 alkyl group that the above-mentioned amino group may have may be substituted by the following groups: phenyl group that is unsubstituted or has one or two substituents selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation, and amino. Examples of phenyl-substituted C1-C4 alkyl groups include benzylamino and aminobenzylamino.

[0185] As a more preferred X 1 and X 2 Examples include: phenylamino groups without substitution or having one or two substituents independently selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation, and amino. X is particularly preferred. 1and X 2 Examples include phenylamino groups having C1-C4 alkoxy groups.

[0186] In equations (1) and (2) above, R 9 This represents a hydrogen atom or a methyl group, preferably a methyl group. m and n each independently represent an integer from 1 to 3, preferably 2.

[0187] When the azo compound or its salt represented by formula (1) is an azo compound or its salt represented by formula (3) below, and the azo compound or its salt represented by formula (2) is an azo compound or its salt represented by formula (4), it is preferred because it can provide a polarizing film with higher transmittance and higher polarization.

[0188]

[0189] In equation (3), R 1 To R 4 Each can independently represent any substituent, and n represents an integer from 1 to 3.

[0190]

[0191] In equation (4), R 5 To R 8 Each can independently represent any substituent, R 9 This represents a hydrogen atom or a methyl group, and n represents an integer from 1 to 3.

[0192] In formulas (3) and (4), the ring structures depicted by the solid and dashed lines represent phenyl (phenylene) or naphthyl (naphthylene).

[0193] In equations (3) and (4), R 1 To R 8 Each can be used to represent any substituent independently. As any substituent, it has the same meaning as the substituents that can be present in equations (1) and (2).

[0194] In equations (1) to (4), m and n independently represent integers from 1 to 3, preferably 2. Furthermore, in equations (2) and (4), R... 9 It represents a hydrogen atom or a methyl group, preferably a methyl group.

[0195] In equations (1) and (3), R 1 To R 4 In formulas (2) and (4), R is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group with a sulfonyl group. 5 To R 8When the polarizing film is independently composed of hydrogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, or C1-C4 alkoxy groups with sulfonyl groups, it is preferred because it can provide a polarizing film with higher transmittance and / or higher polarization.

[0196] As described in Patent Document 10, the general formula of azo compounds or their salts (compound A) represented by formula (1) is mostly represented by formula (1). However, when an amine (Y) is used in the synthesis, it is generally assumed that the amine (Y) is coordinated as shown in formula (5). In this application, the azo compounds or their salts (compound A) represented by formulas (1) and (3) also include those coordinated with an amine (Y), and the desired effect can be achieved regardless of the type of amine (Y) coordinated with them.

[0197] Examples of amines (Y) include ammonia, amino alcohols, hexamethylenetetramine, and pyridine. Monoethanolamine, N-methylethanolamine, diethanolamine, and pyridine are preferred, more preferably monoethanolamine and N-methylethanolamine, and even more preferably N-methylethanolamine.

[0198]

[0199] In equation (5), X 1 Q 1 R 1 To R 4 、m represents the same meaning as in equation (1).

[0200] <Polarizing film>

[0201] The polarizing film of the present invention contains an azo compound represented by formula (1) or a salt thereof (compound A) and an azo compound represented by formula (2) or a salt thereof (compound B) in a substrate, thereby obtaining a polarizing film with excellent (low) cross-transmittance at a wavelength of 730 nm. In one embodiment, the polarizing film of the present invention exhibits high durability in addition to high polarization and high contrast. In one embodiment, the polarizing film of the present invention, etc., has a cross-transmittance (Tc) of 0% or more and 4% or less at a wavelength of 730 nm when the monomer transmittance is 40.5% ± 1%.

[0202] <Substrate>

[0203] The substrate contained in the polarizing film of the present invention is preferably a film obtained by forming a hydrophilic polymer that readily adsorbs compounds (A) and (B) of the present application, dichroic dyes, and especially azo compounds. The hydrophilic polymer is not particularly limited, and examples include polyvinyl alcohol resins, linear starch resins, starch resins, cellulose resins, and polyacrylate resins. Among such resins, from the viewpoint of dyeability, processability, and crosslinking properties of dichroic dyes, polyvinyl alcohol resins or their derivatives are preferred. The shape of the substrate is not particularly limited, and it can be formed into any shape such as a film, sheet, plate, curved plate, or hemispherical. Furthermore, the thickness of the substrate can be appropriately designed according to the application of the polarizing film, preferably in the range of 5 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. The polarizing film of the present invention can be manufactured, for example, by forming the aforementioned hydrophilic polymer as the substrate into a film, then containing compound A, compound B, and other azo compounds or their salts as desired, and then subjecting the resulting film to orientation treatment such as stretching.

[0204] The azo compound represented by formula (1) or its salt (compound A) can be manufactured, for example, by the method described in Patent Document 1. Specific examples of compound A are given below, but are not limited to these. It should be noted that the azo compound is represented in the form of a free acid. Furthermore, the coordination of an amine (Y) as shown in formula (5) is omitted in the following formulas, but any amine can be coordinated.

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211] The azo compound represented by formula (2) or its salt (compound B) can be manufactured by a general azo compound synthesis method, such as the method described in Patent Documents 6 and 7. Specific examples of compound B are given below, but the invention is not limited to these. It should be noted that the azo compound is represented in the form of a free acid. Furthermore, in the polarizing film of the present invention, when the molar number of compound A is set to 1, the molar number of compound B is preferably 0.1 times or more of compound A, more preferably 0.5 times or more, and even more preferably 1 times or more.

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220] Compound A is preferably a green pigment with a maximum absorption wavelength exceeding 640 nm, and compound B is preferably a blue pigment with a maximum absorption wavelength exceeding 600 nm. Furthermore, the polarizing film of the present invention preferably contains one of each of compound A and compound B.

[0221] Regarding the azo compound or its salt (compound A) represented by formula (1) or (3), in the polarizing film containing compound A, when the monomer transmittance is adjusted to Ts = 44.0% ± 0.1%, compound A that satisfies the following condition is preferred. Regarding the presence of λ max The wavelengths (λ1) and (λ2) of the longest wavelength side in the absorption band (with a cross-transmittance Tc value of less than 1.0%) are preferably larger than 650 nm to 750 nm, and more preferably larger than 640 nm to 760 nm. By using compound A having the above-described polarizing film properties, a polarizing film with good polarization characteristics in the long wavelength region can be provided.

[0222] Regarding the azo compound or its salt (compound B) represented by formula (2) or (4), in the polarizing film containing compound B, when the monomer transmittance is adjusted to Ts = 44.0% ± 0.1%, compound B is preferably one that satisfies the following conditions. Regarding the presence of λ max The wavelengths (λ1) and (λ2) of the longest wavelength side in the absorption band (maximum absorption wavelength) with cross-transmittance Tc values ​​less than 1.0% are preferably larger than 600 nm to 650 nm, and more preferably larger than 590 nm to 660 nm.

[0223] When a polarizing film is fabricated by blending multiple dyes, high optical properties are exhibited when the gaps in the absorption waveforms of each dye are filled. Therefore, overlap is preferable between the short wavelength side of the wavelength range of λ1 and λ2 of compound A and the long wavelength side of the wavelength range of λ1 and λ2 of compound B. Thus, by combining the above-mentioned compounds A and B, a polarizing film with high optical properties can be provided, in which the gaps in the absorption waveforms of each dye are filled and sufficient polarization characteristics are exhibited at 730 nm.

[0224] The polarizing film of the present invention preferably contains one or more dichroic dyes other than compound A and compound B. As the dichroic dyes, it is preferred to blend a dichroic dye (hereinafter referred to as compound C) that has absorption primarily in the short wavelength region ranging from yellow to orange and a dichroic dye (hereinafter referred to as compound D) that has absorption primarily in the red to purple region. It is preferred to blend one of each of compound C and compound D. The polarizing film of the present invention exhibits high polarization and high contrast over a wider wavelength range than conventional dye-based polarizing films. Furthermore, compared to conventional dye-based polarizing plates, polarizing plates containing this polarizing film exhibit high durability against heat, humidity, and light.

[0225] For the polarizing film of the present invention, compounds C of dichroic dyes that are primarily yellow to orange and have a maximum absorption wavelength of 400 nm or more but less than 500 nm are preferred examples of which are azo compounds. Examples include commercially available CI Direct Yellow 12, CI Direct Yellow 28, CI Direct Yellow 44, CI Direct Orange 26, CI Direct Orange 39, CI Direct Orange 71, CI Direct Orange 107, etc. Furthermore, stilbene orange dyes of formula (2) described in Example 1 of International Publication No. 2007 / 138980, urea orange dyes described in International Publication No. 2018 / 181470, and International Publication No. 2019 / 124161 may be used, but are not limited thereto.

[0226]

[0227]

[0228] Compound D, which is a dichroic dye primarily ranging from red to purple with a maximum absorption wavelength of 500 nm or more but less than 600 nm and can be used in the polarizing film of the present invention, is preferably an azo compound. Examples of commercially available compounds include CI Direct Red 2, CI Direct Red 31, CI Direct Red 79, CI Direct Red 81, CI Direct Red 117, and CI Direct Red 247. Furthermore, urea-based red dyes described in International Publication Nos. 2016 / 186194, 2016 / 186195, and 2016 / 186196, as well as 1-naphthol-3-sulfonic acid (J acid)-based red dyes described in Japanese Patent Application Publication Nos. 08-291259, 2002-275381, and 2017 / 135391, may be used, but the invention is not limited to these.

[0229]

[0230] The azo compounds represented by formulas (1) to (5) above, and the dichroic dyes used in combination, can be in the form of free acids, salts, or salts of metal ions or ammonium ions. Examples of metal ions include alkali metal ions such as lithium ions, sodium ions, and potassium ions, as well as alkaline earth metal ions such as calcium ions and magnesium ions. Examples of ammonium ions include ammonium ions, methylammonium ions, dimethylammonium ions, triethylammonium ions, tetraethylammonium ions, tetra-n-propylammonium ions, tetra-n-butylammonium ions, monoethanolammonium ions, diethanolammonium ions, triethanolammonium ions, and N-methyl-N-monoethanolammonium ions. More specifically, for example, free acids are represented by sulfonic acid (-SO3H), sodium ions by sodium sulfonate (-SO3Na), and ammonium ions by ammonium sulfonate (-SO3NH4).

[0231] In the polarizing film of the present invention, the mixing ratio of the azo compounds used is preferably adjusted such that the transmittance falls within the preferred range described later. The polarizing performance of the polarizing film varies not only due to the mixing ratio of each azo compound in the polarizing film, but also due to various factors such as the swelling degree of the substrate adsorbing the azo compounds, the stretching ratio, the dyeing time, the dyeing temperature, the pH during dyeing, and the influence of salt. Therefore, such mixing ratios can be appropriately adjusted based on the description described later.

[0232] (Visual perception correction transmittance)

[0233] The transmittance of the polarizing film and polarizing plate of the present invention was determined in accordance with JIS Z 8722:2009.

[0234] (Visual sensitivity correction for single-cell transmittance)

[0235] The polarizing film and polarizing plate of the present invention preferably have a single-unit transmittance of 35% to 70% in the wavelength range of 380 nm to 780 nm. Single-unit transmittance is the transmittance obtained by performing visual sensitivity correction on a single test sample (e.g., a polarizing film or polarizing plate) according to JIS Z 8722:2009. Higher transmittance is required for the performance of a polarizing plate, but as long as the single-unit transmittance is 35% to 70%, even if a polarizing film with this single-unit transmittance is used in a display device, brightness can be displayed without any sense of incongruity. When the single-unit transmittance exceeds 70%, the polarization degree sometimes decreases significantly, which is not preferred. On the other hand, there is a tendency for higher transmittance to decrease polarization degree; therefore, from the viewpoint of balancing with polarization degree, a single-unit transmittance of 35% to 60% is more preferred, further preferred is 37% to 55%, and particularly preferred is 39% to 50%.

[0236] The polarization degree of the polarizing film and polarizing plate is preferably 50% to 100%, more preferably 80% to 100%, even more preferably 95% to 100%, and particularly preferably 99% to 100%. The higher the polarization degree, the better. In the relationship between polarization degree and transmittance, the transmittance and polarization degree can be adjusted to a suitable level by emphasizing brightness or polarization degree (or contrast), so that it can be applied to display devices, etc.

[0237] Regarding the absorption band, if the transmittance is adjusted within the 400 to 700 nm range, light leakage occurs on the longer wavelength side, resulting in a decrease in actual contrast (degraded display quality). To suppress this, it is preferable to have a uniform absorption band within the 380 to 780 nm range. For example, to effectively address light leakage on the longer wavelength side above 700 nm, it is preferable to adjust the transmittance at the cross-section above 700 nm, specifically adjusting the transmittance at the cross-section of 730 nm. The transmittance is preferably 0 to 20%, more preferably 0 to 4%, and even more preferably 0 to 1%.

[0238] Next, taking the case of fabricating a polarizing film by adsorbing an azo compound onto a substrate made of polyvinyl alcohol resin as an example, a specific method for manufacturing a polarizing film will be described. It should be noted that the method for manufacturing the polarizing film of the present invention is not limited to the following method.

[0239] (Preparation of the preform film)

[0240] The film that forms the basis of the substrate film (hereinafter referred to as the preform film or film) can be made by forming a film from a polyvinyl alcohol (PVA) resin. There are no particular limitations on the PVA resin; commercially available PVA resins or PVA resins synthesized by known methods can be used. For example, a PVA resin can be obtained by saponifying a polyvinyl acetate (PVC) resin. Examples of PVC resins include, in addition to PVC as a homopolymer of PVC, copolymers of PVC and other monomers that can be copolymerized with it. Examples of other monomers that can be copolymerized with PVC include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The degree of saponification of the PVA resin is generally preferably about 85 to 100 mol%, more preferably 95 mol% or more. The PVA resin can be further modified; for example, aldehyde-modified PVA formal or PVA acetal can also be used. Furthermore, the degree of polymerization of polyvinyl alcohol resins refers to the viscosity-uniform degree of polymerization, which can be determined by methods known in the art. It is generally preferred to be around 1,000 to 10,000, and more preferably around 1,500 to 6,000.

[0241] There are no particular limitations on the method for forming films from polyvinyl alcohol (PVA)-based resins, and known methods can be used. In this case, the PVA-based resin film may also contain glycerol, ethylene glycol, propylene glycol, low molecular weight polyethylene glycol, etc., as plasticizers. The content of the plasticizer relative to the total film is preferably 5 to 20% by weight, more preferably 8 to 15% by weight. The film thickness of the preform film is not particularly limited, for example, it is about 5 μm to 150 μm, preferably about 10 μm to 100 μm.

[0242] (Swelling process)

[0243] The obtained preform film is subjected to a swelling treatment. The swelling treatment is preferably performed by immersing the preform film in a solution at 20 to 50°C for 30 seconds to 10 minutes; the solution is preferably water. The stretch ratio of the swollen preform film is preferably adjusted to 1.00 to 1.50 times, more preferably to 1.10 to 1.35 times. In cases where the manufacturing time of the polarizing film is shortened, the preform film also swells during the dyeing process described later, so the swelling treatment can be omitted.

[0244] (Dyeing process)

[0245] Next, a dyeing process is performed to adsorb and impregnate the membrane obtained by the swelling treatment with the azo compound or dichroic dye of the present invention. If the swelling process is omitted, the swelling treatment of the preform membrane can be performed simultaneously during the dyeing process. During the dyeing process, for example, the color of the resin membrane can be adjusted using azo compound as a dichroic dye, as illustrated in Masahiro Irie, "Applications of Functional Pigments," First Printing Edition, CMC Co., Ltd., June 2002, pp. 98-100, to a degree that does not impair the performance of the polarizing film of the present invention.

[0246] The dyeing process is not particularly limited as long as the method of adsorbing and impregnating the azo compound, which is a dichroic dye, onto the membrane is not particularly limited. For example, it is preferable to color the membrane by immersing it in a dyeing solution. Alternatively, it can be colored by coating the membrane with the dyeing solution. The concentration of each azo compound in the dyeing solution is not particularly limited as long as the membrane is sufficiently colored. For example, it can be adjusted in the range of 0.05 g / L to 100 g / L.

[0247] The temperature of the dyeing solution in the dyeing process is preferably 5 to 60°C, more preferably 20 to 50°C, and particularly preferably 35 to 50°C. Furthermore, the immersion time of the membrane in the dyeing solution can be appropriately adjusted, preferably between 30 seconds and 20 minutes, more preferably between 1 and 10 minutes.

[0248] In addition to the azo compound used in this invention, the dyeing solution may further contain dyeing auxiliaries as needed. Examples of dyeing auxiliaries include sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate, anhydrous sodium sulfate, and sodium tripolyphosphate. The content of the dyeing auxiliaries can be adjusted arbitrarily according to the above-mentioned immersion time and the temperature of the dyeing solution based on the dyeing properties of the dye used, and is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight in the dyeing solution.

[0249] (Cleaning Step 1)

[0250] After the dyeing process, a cleaning process (hereinafter also referred to as "cleaning process 1") can be performed to remove the dyeing solution adhering to the surface of the resin film. By performing cleaning process 1, the transfer of dye remaining on the surface of the resin film to the liquid to be processed next can be inhibited. In cleaning process 1, water is usually used as the cleaning solution. The preferred cleaning method is to immerse the dyed resin film in the cleaning solution; on the other hand, cleaning can also be performed by applying the cleaning solution to the resin film. The cleaning time is not particularly limited, but is preferably 1 to 300 seconds, more preferably 1 to 60 seconds. The temperature of the cleaning solution in cleaning process 1 needs to be at a temperature at which the material constituting the resin film (e.g., a hydrophilic polymer, here polyvinyl alcohol-based resin) is insoluble, and the cleaning treatment is usually performed at 5 to 40°C. However, even without cleaning process 1, the performance of the polarizing film will not be affected, so cleaning process 1 can be omitted.

[0251] (The process of making the membrane contain crosslinking agents and / or water-resistant agents)

[0252] After the dyeing or washing step 1, a crosslinking agent and / or a water-resistant agent may be included. The method of including the crosslinking agent and / or water-resistant agent in the resin film is preferably to immerse the resin film in a treatment solution containing the crosslinking agent and / or water-resistant agent; alternatively, the treatment solution may be coated or applied to the resin film. The treatment solution contains at least one crosslinking agent and / or water-resistant agent and a solvent. The temperature of the treatment solution is preferably 5 to 70°C, more preferably 5 to 50°C. Furthermore, the treatment time in this step is preferably 30 seconds to 6 minutes, more preferably 1 to 5 minutes.

[0253] As a crosslinking agent, boron compounds such as boric acid, borax, or ammonium borate, polyaldehydes such as glyoxal or glutaraldehyde, polyisocyanate compounds such as biuret, isocyanurate, or end-capped polyisocyanates, and titanium compounds such as titanium oxysulfate can be used. Additionally, ethylene glycol glycidyl ether and polyamide epichlorohydrin can also be used. As a water-resistant agent, examples include succinic acid peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glyceryl diglycidyl ether, ammonium chloride, or magnesium chloride, with boric acid being preferred. The solvent used for the crosslinking agent and / or water-resistant agent is not particularly limited, but water is preferred. The concentration of the crosslinking agent and / or water-resistant agent in the treatment solution can be appropriately determined according to their type. For example, when using boric acid, the concentration of boric acid in the treatment solution is preferably 0.1 to 6.0% by weight, more preferably 1.0 to 4.0% by weight. It should be noted that if it is desired to shorten the manufacturing time of the polarizing film, or if crosslinking treatment or water-resistant treatment is not required, this treatment step can be omitted.

[0254] (Stretching process)

[0255] After the dyeing process, or optionally after the washing process 1 or a process containing a crosslinking agent and / or a water-resistant agent, a stretching process is performed. The stretching process is performed by uniaxial stretching of the resin film. The stretching method can be either dry stretching or wet stretching. The stretching ratio is preferably 3 times or more, more preferably 5 to 8 times.

[0256] In the dry stretching process, when the heating medium is air, it is preferable to stretch the resin film at a temperature between room temperature and 180°C. Furthermore, the humidity is preferably in an atmosphere of 20% to 95% RH. Examples of heating methods for the resin film include, but are not limited to, inter-roll stretching, roller-heated stretching, hot-press stretching, and infrared heating stretching. The dry stretching process can be performed in a single stage or in multiple stages (two or more stages).

[0257] In the wet stretching process, the resin film is preferably stretched in water, a water-soluble organic solvent, or a mixture thereof. More preferably, the stretching process is performed while immersing the resin film in a solution containing at least one crosslinking agent and / or a water-resistant agent. The crosslinking agent and water-resistant agent can be those described above in the steps containing the crosslinking agent and / or water-resistant agent. The concentration of the crosslinking agent and / or water-resistant agent in the solution during the stretching process is preferably 0.5 to 15% by weight, more preferably 2.0 to 8.0% by weight. The stretching temperature is preferably 40 to 60°C, more preferably 45 to 58°C. The stretching time is typically 30 seconds to 20 minutes, preferably 2 to 5 minutes. The wet stretching process can be carried out by a single-stage stretching or by a multi-stage stretching process involving two or more stages.

[0258] (Cleaning Step 2)

[0259] After the stretching process, crosslinking agents and / or water-resistant agents may sometimes precipitate on the surface of the resin film, or foreign matter may adhere. Therefore, a cleaning process (hereinafter also referred to as "cleaning process 2") can optionally be performed to clean the surface of the resin film. The cleaning time is preferably 1 second to 5 minutes. The cleaning method preferably involves immersing the resin film in a cleaning solution; alternatively, cleaning can also be performed by coating or applying the cleaning solution to the resin film. Water is preferred as the cleaning solution. The cleaning process can be performed in one stage or in a multi-stage process of two or more stages. The temperature of the cleaning solution in the cleaning process is not particularly limited, but is generally 5 to 50°C, preferably 10 to 40°C.

[0260] In addition to water, other processing solutions or solvents used in the above-described processing steps may include, for example, alcohols such as dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropanol, glycerol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or trimethylolpropane, as well as amines such as ethylenediamine and diethylenetriamine. The processing solution or solvent is not limited to these, but water is most preferred. Furthermore, one of these processing solutions or solvents may be used alone, or a mixture of two or more may be used.

[0261] (Drying process)

[0262] After the stretching or cleaning step 2, a drying process is performed on the resin film. Drying can be carried out naturally, but to further improve drying efficiency, it can be achieved by compression using rollers, removal of surface moisture using air knives or suction rollers, or by forced-air drying. The drying temperature is preferably 20 to 100°C, more preferably 60 to 100°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 5 to 10 minutes.

[0263] (Polarizing plate)

[0264] The polarizing plate of the present invention comprises: a polarizing film containing the aforementioned azo compound in a preform film, and a transparent protective layer disposed on one or both sides of the polarizing film. The transparent protective layer is used to improve the water resistance, operability, etc. of the polarizing film.

[0265] A transparent protective layer is a protective film formed using a transparent material. The protective film is a layered film capable of maintaining the shape of a polarizing film, and is preferably made of plastics with excellent transparency, mechanical strength, thermal stability, and moisture barrier properties. Alternatively, protective films formed from other materials that possess functions equivalent to such plastics can also be used. Examples of plastics constituting the protective film include films made from thermoplastic resins such as polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, or acrylic resins; thermosetting resins such as acrylic, urethane, and acrylic-based urethane resins; epoxy or silicone resins; or UV-curable resins. Among these, polyolefin resins include amorphous polyolefin resins containing polymeric units of cyclic polyolefins such as norbornene monomers or polycyclic norbornene monomers. Generally, a protective film that does not impede the performance of the polarizing film is preferred. Cellulose triacetate (TAC) or norbornene resins formed from cellulose acetate-based resins are particularly preferred. Furthermore, the protective film may undergo hard coating, anti-reflective treatment, or treatments for purposes such as preventing adhesion, diffusion, or glare, as long as the effects of the invention are not compromised. The thickness of the transparent protective layer can be appropriately designed according to the application of the polarizing film, preferably in the range of 1 μm to 200 μm, more preferably in the range of 5 μm to 150 μm, and particularly preferably in the range of 10 μm to 100 μm.

[0266] The polarizing plate preferably further comprises an adhesive layer between the transparent protective layer and the polarizing film for bonding the transparent protective layer to the polarizing film. The adhesive constituting the adhesive layer is not particularly limited, but a polyvinyl alcohol (PVA) based adhesive is preferred. Examples of PVA based adhesives include EXCEVAL RS-2117 (manufactured by Kuraray), but it is not limited to these. Furthermore, a crosslinking agent and / or a water-resistant agent may be added to the adhesive. As the polymer constituting the PVA based adhesive, a maleic anhydride-isobutylene copolymer is preferred, but an adhesive mixed with a crosslinking agent may also be used as needed. Examples of maleic anhydride-isobutylene copolymers include ISOBAM#18 (manufactured by Kuraray), ISOBAM#04 (manufactured by Kuraray), ammonia-modified ISOBAM#104 (manufactured by Kuraray), ammonia-modified ISOBAM#110 (manufactured by Kuraray), imidized ISOBAM#304 (manufactured by Kuraray), and imidized ISOBAM#310 (manufactured by Kuraray). Water-soluble polyepoxide compounds can be used as crosslinking agents. Examples of water-soluble polyepoxide compounds include Denacol EX-521 (manufactured by Nagase ChemteX) and Tetrad-C (manufactured by Mitsubishi Gas Chemical). Furthermore, known adhesives such as urethane-based, acrylic-based, and epoxy-based adhesives can be used as adhesives other than polyvinyl alcohol-based resins. Acetylacetyl-modified polyvinyl alcohol is particularly preferred, and furthermore, polyaldehydes are preferably used as crosslinking agents. Furthermore, from the viewpoint of improving the adhesive's bonding strength or water resistance, additives such as zinc compounds, chlorides, or iodides can be used alone or in combination and included in the adhesive at a concentration of approximately 0.1 to 10% by weight. There are no particular limitations on the additives that can be included in the adhesive; they can be selected appropriately. After bonding the transparent protective layer to the polarizing film using the adhesive, a polarizing plate can be produced by drying or heat-treating it at an appropriate temperature.

[0267] When a polarizing plate is bonded to a display device such as a liquid crystal display (LCD) or an organic light-emitting diode (OLED), various functional layers, brightness-enhancing layers, or films may be applied to the surface of a transparent protective layer or film that subsequently becomes a non-exposed surface. These functional layers may include, for example, layers or films for controlling phase difference. The polarizing plate is preferably bonded to these films or the display device using an adhesive.

[0268] Furthermore, the polarizing plate may appropriately possess various known functional layers, such as anti-reflective layers, anti-glare layers, or hard coatings, on the exposed surface of the protective layer or protective film. When manufacturing such functional layers, it is preferable to apply various functional materials to the exposed surface of the protective layer or protective film. Alternatively, such functional layers or films may be bonded to the exposed surface of the protective layer or protective film using adhesives or bonding agents.

[0269] The polarizing film or polarizing plate of the present invention may be provided with a protective layer and / or a functional layer, as well as a transparent support such as glass, crystal, or sapphire, as needed. Furthermore, it can be applied to liquid crystal projectors, calculators, clocks, laptops, word processors, LCD TVs, polarizing lenses, polarizing glasses, car navigation systems, indoor and outdoor measuring instruments, displays, etc., but is not limited to these. The polarizing film or polarizing plate of the present invention is particularly suitable for use in display devices, such as reflective liquid crystal displays, translucent liquid crystal displays, or organic electroluminescent displays. Display devices using the polarizing film or polarizing plate of the present invention can display high-quality white and neutral black, similar to paper. Furthermore, display devices using the polarizing film or polarizing plate of the present invention are display devices with high durability, high reliability, long-term high contrast, and high color reproduction.

[0270] The present invention will be described in detail below through examples, but the present invention is not limited to these examples. Unless otherwise specified, % and parts in the examples are based on weight.

[0271] [Example 1]

[0272] <Synthesis example>

[0273] (Process 1)

[0274] The tetraazo compound represented by formula (6) was obtained by the method described in International Publication No. 2012 / 108169.

[0275]

[0276] (Process 2)

[0277] 38.2 parts of the tetraazo compound obtained in step 1 were added to 900 parts of water and stirred to suspend it. 28.4 parts of monoethanolamine and 11.3 parts of copper sulfate pentahydrate were added to this mixture and reacted at 90 to 98°C for 10 hours to complete the copperization reaction. After salting out with sodium chloride, the mixture was filtered and dried to obtain 7.0 parts of the compound with the amine coordinated to the azo compound represented by compound example A-1. Furthermore, the above-mentioned amine coordinated to the above-mentioned azo compound is shown in formula (7).

[0278]

[0279] <Fabrication of Polarizing Film and Polarizing Plate>

[0280] A polyvinyl alcohol resin film (“VF-PE#6000” manufactured by Kuraray Co., Ltd.; hereinafter referred to as “film”) with a saponification degree of 99 mol% or more and a film thickness of 60 μm was immersed in warm water at 35°C for 3 minutes to perform a swelling treatment. The swollen film was immersed in an aqueous solution at 48°C for 10 minutes containing 1.1 parts by weight of an azo compound represented by compound example A-1 (in the form of amine coordination formula (7)) as compound A, 1.5 parts by weight of an azo compound represented by compound example B-1 as compound B, 0.1 parts by weight of an azo compound represented by compound example C-1 as compound C, 0.8 parts by weight of an azo compound represented by compound example D-1 as compound D, 1.5 parts by weight of sodium tripolyphosphate, 1.5 parts by weight of anhydrous sodium sulfate, and 1500 parts by weight of water, so that it contains azo compounds. The membrane containing the azo compound was cleaned with water, and after cleaning, it was subjected to a boric acid-based crosslinking treatment for 1 minute in an aqueous solution containing 2.7% by weight of boric acid at 40°C. The crosslinked membrane was then stretched to 6.0 times its original length while being subjected to a crosslinking treatment in an aqueous solution containing 3.0% by weight of boric acid at 58°C for 5 minutes. While maintaining the tension of the stretched membrane, it was cleaned in room temperature water for 10 seconds. The cleaned membrane was then immediately dried at 70°C for 3 minutes to obtain a polarizing film. The polarizing film of the present invention containing an azo compound having the structure of formula (1) and an azo compound having the structure of formula (2) was prepared by the above method. Using a polyvinyl alcohol adhesive, a 60 μm thick triacetate cellulose membrane (TG-60UL, Fujifilm, hereinafter referred to as "TAC") treated with alkali as a transparent protective layer was laminated onto both sides of the polarizing film, thereby preparing the polarizing plate of the present invention comprising TAC / adhesive layer / polarizing film / adhesive layer / TAC. The resulting polarizing plate maintains the optical properties of the aforementioned polarizing film, especially monomer transmittance, hue, and polarization. This polarizing plate was used as the test sample in Example 1.

[0281] [Example 2]

[0282] <Synthesis example>

[0283] In step 2 of the synthesis example of Example 1, except that 28.4 parts of N-methylethanolamine were used instead of 28.4 parts of monoethanolamine, 8.7 parts of the azo compound represented by Compound Example A-1 were obtained by the same method as in Example 1. It should be noted that the above-mentioned amine is coordinated to the above-mentioned azo compound in the form shown in Formula (8).

[0284]

[0285] <Fabrication of Polarizing Film and Polarizing Plate>

[0286] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with: "0.7 parts by weight of an azo compound represented by [Compound Example A-1] (formula (8)) as amine coordination as compound A, 0.9 parts by weight of an azo compound represented by [Compound Example B-55] as compound B, 0.1 parts by weight of an azo compound represented by [Compound Example C-1] as compound C, and 0.7 parts by weight of an azo compound represented by [Compound Example D-1] as compound D". Otherwise, the polarizing plate was fabricated using the same method as the fabrication of the polarizing film and polarizing plate in Example 1.

[0287] [Example 3]

[0288] <Fabrication of Polarizing Film and Polarizing Plate>

[0289] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with: "1.5 parts by weight of an azo compound represented by [Compound Example A-1] (formula (7)) as amine coordination as compound A, 1.8 parts by weight of an azo compound represented by [Compound Example B-1] as compound B, 0.1 parts by weight of an azo compound represented by [Compound Example C-3] as compound C, and 0.8 parts by weight of an azo compound represented by [Compound Example D-1] as compound D". Otherwise, the polarizing plate was fabricated using the same method as the fabrication of the polarizing film and polarizing plate in Example 1.

[0290] [Example 4]

[0291] <Fabrication of Polarizing Film and Polarizing Plate>

[0292] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with: 1.5 parts by weight of an azo compound represented by [Compound Example A-1] (formula (8)) as amine coordination, 2.4 parts by weight of an azo compound represented by [Compound Example B-1] as compound B, 0.1 parts by weight of an azo compound represented by [Compound Example C-1] as compound C, and 0.6 parts by weight of an azo compound represented by [Compound Example D-1] as compound D. Otherwise, the polarizing plate was fabricated using the same method as the fabrication of the polarizing film and polarizing plate in Example 1.

[0293] [Comparative Example 1]

[0294] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with the compounds represented by formulas (9) and (10) described in Example 8 of Patent Document 1, CI Direct Orange 39, and CI Direct Red 117. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. Specifically, four dichroic dyes were used, and the polarizing plate was composed of the compounds represented by formulas (9) and (10) as dyes replacing compounds A and B, CI Direct Orange 39 as compound C, and CI Direct Red 117 as compound D.

[0295]

[0296] [Comparative Example 2]

[0297] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with compounds represented by formulas (11) and (12) as described in Example 87 of Patent Document 2, and compounds described as [Compound Example C-1] and [Compound Example D-1]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate is composed of compounds represented by formulas (11) and (12) as dyes replacing compounds A and B, [Compound Example C-1] as compound C, and [Compound Example D-1] as compound D.

[0298]

[0299] [Comparative Example 3]

[0300] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with compounds represented by formulas (9) and (13) as described in Example 19 of Patent Document 3, and compounds described as [Compound Example C-1] and [Compound Example D-2]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, the polarizing plate was composed of compounds represented by formulas (9) and (13) as dyes replacing compounds A and B, [Compound Example C-1] as compound C, and [Compound Example D-1] as compound D.

[0301]

[0302] [Comparative Example 4]

[0303] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with compounds represented by formulas (11) and (13) as described in Example 13 of Patent Document 3, Compound Example C-1, and CI Direct Red 117. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, the polarizing plate was composed of compounds represented by formulas (11) and (13) as dyes replacing compounds A and B, [Compound Example C-1] as compound C, and [Compound D-1] as compound D.

[0304]

[0305] [Comparative Example 5]

[0306] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with compounds represented by formulas (6) and (14) as described in Example B1 of Patent Document 4, CI Direct Orange 39, and [Compound Example D-3]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, the polarizing plate is composed of compounds represented by formulas (6) and (14) as dyes replacing compounds A and B, CI Direct Orange 39 as compound C, and [Compound Example D-3] as compound D.

[0307]

[0308] [Comparative Example 6]

[0309] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with three compounds described in Example 18 of Patent Document 2, represented by the following formula (6), [Compound Example C-1], and [Compound Example D-1]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate does not use compound A, but is composed of the compound represented by the following formula (6) as a dye replacing compound B, [Compound Example C-1] as compound C, and [Compound Example D-3] as compound D.

[0310]

[0311] [Comparative Example 7]

[0312] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with three compounds described in Example 4 of Patent Document 1, represented by the following formula (15), [Compound Example C-1], and CI Direct Red 117. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate does not use compound B and is composed of a compound represented by the following formula (15) as a dye replacing compound A, [Compound Example C-1] as compound C, and CI Direct Red 117 as compound D.

[0313]

[0314] [Comparative Example 8]

[0315] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with three compounds represented by the following formula (16) as described in Example 6 of Patent Document 5, [Compound Example C-1], and [Compound Example D-4]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate does not use compound A, but is composed of the compound represented by the following formula (16) as a dye replacing compound B, [Compound Example C-1] as compound C, and [Compound Example D-4] as compound D.

[0316]

[0317] [Comparative Example 9]

[0318] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with three compounds described in Example 3 of Patent Document 9, represented by the following formula (17), CI Direct Orange 39, and [Compound Example D-5]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate does not use compound A, but is composed of the compound represented by the following formula (17) as a dye replacing compound B, CI Direct Orange 39 as compound C, and [Compound Example D-5] as compound D.

[0319]

[0320] [Comparative Example 10]

[0321] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with three compounds represented by the following formula (18) as described in Example 22 of Patent Document 10, [Compound Example C-2], and [Compound Example D-6]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate does not use compound A, but is composed of the compound represented by the following formula (18) as a dye replacing compound B, [Compound Example C-2] as compound C, and [Compound Example D-6] as compound D.

[0322]

[0323] [Comparative Example 11]

[0324] The four compounds used in the fabrication of the polarizing film in Example 1 were replaced with three compounds described in Example 3 of Patent Document 11, represented by the following formula (19), CI Direct Orange 39, and [Compound Example D-7]. Otherwise, the polarizing plate was fabricated using the same method as in Example 1. That is, this polarizing plate does not use compound A, but is composed of the compound represented by the following formula (19) as a dye replacing compound B, CI Direct Orange 39 as compound C, and [Compound Example D-7] as compound D.

[0325]

[0326] [Comparative Example 12]

[0327] Except for changing the weight parts of the dye used in Comparative Example 6, the polarizing plate was manufactured in the same manner. Specifically, the amount of the azo compound represented by Formula (6) was changed to 2.0 parts by weight, the amount of the azo compound represented by [Compound Example C-1] was changed to 0.1 parts by weight, and the amount of the azo compound represented by [Compound Example D-1] was changed to 0.3 parts by weight. By changing the weight parts, a polarizing plate with a monomer transmittance of 40.1% was obtained.

[0328] [Comparative Example 13]

[0329] Except for changing the weight parts of the dye used in Comparative Example 10, the polarizing plate was prepared using the same method. Specifically, the amount of the azo compound represented by the above formula (18) was changed to 1.5 parts by weight, the amount of the azo compound represented by [Compound Example C-2] was changed to 1.5 parts by weight, and the amount of the azo compound represented by [Compound Example D-6] was changed to 0.9 parts by weight. By changing the weight parts, a polarizing plate with a monomer transmittance of 40.1% was obtained.

[0330] [Reference Example 1A]

[0331] <Production of Polarizing Film>

[0332] A polyvinyl alcohol resin membrane (“VF-PE#6000” manufactured by Kuraray Co., Ltd.; hereinafter referred to as “membrane”) with a saponification degree of 99 mol% or more and a membrane thickness of 60 μm was immersed in warm water at 35°C for 3 minutes to perform a swelling treatment. The swollen membrane was immersed in an aqueous solution at 48°C for 2 to 5 minutes with a monomer permeability Ts = 44.0% ± 0.1% containing 0.45 parts by weight of an azo compound represented by [Compound Example A-1] (in the form of amine coordination formula (7)), 1.5 parts by weight of sodium tripolyphosphate, 1.5 parts by weight of anhydrous sodium sulfate, and 1500 parts by weight of water to contain the azo compound. The membrane containing the azo compound was washed with water, and after washing, it was subjected to a boric acid-based crosslinking treatment at 40°C for 1 minute with an aqueous solution containing 2.7% by weight of boric acid. The cross-linked membrane was subjected to cross-linking treatment in an aqueous solution containing 3.0% by weight of boric acid at 55°C for 5 minutes, while being stretched to 5.0 times its original length. While maintaining the stretched membrane under tension, it was washed in room temperature water for 10 seconds. The washed membrane was then immediately dried at 70°C for 3 minutes to obtain the polarizing film.

[0333] [Refer to Example 2A]

[0334] <Production of Polarizing Film>

[0335] The azo compound used in the fabrication of the polarizing film in Reference Example 1A was replaced with 0.45 parts by weight of an azo compound represented as [Compound Example A-1] (formula (8) in amine coordination form). Otherwise, the polarizing film was fabricated using the same method as that used in the fabrication of the polarizing film in Reference Example 1A.

[0336] [Refer to Example 1B]

[0337] <Production of Polarizing Film>

[0338] The azo compound used in the fabrication of the polarizing film in Reference Example 1A was replaced with 0.45 parts by weight of the azo compound represented by [Compound Example B-1]. Otherwise, the polarizing film was fabricated using the same method as that used in the fabrication of the polarizing film in Reference Example 1A.

[0339] [Refer to Example 2B]

[0340] <Production of Polarizing Film>

[0341] The azo compound used in the fabrication of the polarizing film in Reference Example 1A was replaced with 0.45 parts by weight of the azo compound represented by [Compound Example B-55]. Otherwise, the polarizing film was fabricated using the same method as that used in the fabrication of the polarizing film in Reference Example 1A.

[0342] [Comparative Example 1A]

[0343] <Production of Polarizing Film>

[0344] The azo compound used in the fabrication of the polarizing film in Reference Example 1A was replaced with 0.45 parts by weight of the azo compound represented by the above formula (10). Otherwise, the polarizing film was fabricated using the same method as that used in the fabrication of the polarizing film in Reference Example 1A.

[0345] [Comparative Example 1B]

[0346] <Production of Polarizing Film>

[0347] The azo compound used in the fabrication of the polarizing film in Reference Example 1A was replaced with 0.45 parts by weight of the azo compound represented by the above formula (9). Otherwise, the polarizing film was fabricated using the same method as that used in the fabrication of the polarizing film in Reference Example 1A.

[0348] <Evaluation>

[0349] The test samples obtained in Reference Examples 1A to 2A, 1B to 2B, Examples 1 to 4 and Comparative Examples 1A, 1B, 1 to 13 were evaluated in the following manner.

[0350] <Polarized parallel transmittance Ky, polarized orthogonal transmittance Kz>

[0351] The parallel transmittance (Ky) and orthogonal transmittance (Kz) of polarized light for each test sample were determined using a spectrophotometer (Hitachi High-Tech UH-4150). Here, Ky refers to the transmittance when the absorption axis of the absolute polarizer is parallel to the absorption axis of the polarizing film or polarizing plate, and Kz represents the transmittance when the absorption axis of the absolute polarizer is orthogonally superimposed to the absorption axis of the polarizing plate or polarizing film. Ky and Kz were measured at 1 nm wavelength intervals in the range of 380 to 780 nm (or 400 to 700 nm, or 730 nm).

[0352] <Single-cell transmittance Ts, parallel-position transmittance Tp, and orthorhombic transmittance Tc>

[0353] Single-unit transmittance Ts is the spectral transmittance at each wavelength when measured with a single test sample. Parallel-position transmittance Tp is the spectral transmittance at each wavelength when two test samples are superimposed with their absorption axes parallel. Orthogonal-position transmittance Tc is the spectral transmittance when two polarizing plates are superimposed with their absorption axes orthogonal. Using Ky and Kz obtained by measurement at 380 to 780 nm, various transmittances at 380 to 780 nm (or 400 to 700 nm, or 730 nm) are calculated using the following formulas (i) to (iii).

[0354]

[0355] <Visual Sensitivity Correction Single Cell Transmittance Ys> 380至780 Or Ys 400至700 Visual perception correction parallel position transmittance Yp 380至780 or Yp 400至700 and visual sensitivity correction orthogonal position transmittance Yc 380至780 or Yc 400至700 >

[0356] Visual sensitivity correction monomer transmittance Ys 380至780 Visual perception correction parallel position transmittance Yp 380至780 and visual sensitivity correction orthogonal transmittance Yc 380至780 This refers to the transmittance Ts of a single unit, Tp of a parallel position, and Tc of a cross-section, calculated at specified wavelength intervals dλ in the wavelength region from 380 to 780 nm, after visual sensitivity correction according to JIS Z 8722:2009. Specifically, the transmittance Ts of a single unit, Tp of a parallel position, and Tc of a cross-section are substituted into the following formula to calculate them respectively. It should be noted that in the following formula, Pλ represents the spectral distribution of the standard light (C light source), and yλ represents the isochromatic function of a 2-degree field of view. It should also be noted that when setting the wavelength region, the spectral distribution and isochromatic function of the standard light used must also be set to the same wavelength region.

[0357] Formulas (1) to (3) are the various transmittances (Ys) when the wavelength range is set to 380 to 780 nm. 380~780 Yp 380~780 Yc 380~780 The calculation formula for ).

[0358]

[0359] Similar to patent documents 2, 4, and 9, the wavelength range is set to 400 to 700 nm for evaluation. It should be noted that calculation formulas (4) to (6) are for various transmittances (Ys) when the wavelength range is set to 400 to 700 nm according to calculation formulas (1) to (3). 400~700 Yp 400~700 Yc 400~700 The calculation formula for ).

[0360]

[0361] <polarization degree ρy 380至780 or ρy 400至700 >

[0362] For each sample being measured, the polarization ρy is calculated. 380~780 or ρy400~700 . Polarization degree ρy 380~780 As shown in formula (7), the polarization ρy 400~700 The calculation is shown in equation (8). The polarization is substituted into the visual sensitivity correction parallel transmittance Yp. 380~780 or Yp 400~700 and visual sensitivity correction orthogonal transmittance Yc 380~780 or Yc 400~700 And calculated.

[0363]

[0364] Contrast

[0365] Visual perception correction parallel transmittance Yp 380~780 or Yp 400~700 Orthogonal transmittance Yc with visual sensitivity correction 380~780 or Yc 400~700 Substituting into formula (9) or (10), we obtain the contrast ratio (CR). 380~780 or CR 400~700 ).

[0366]

[0367] Table 1A shows the monomer transmittance Ts = 44.0% ± 0.1% for each test sample prepared in Reference Examples 1A to 2A and Comparative Example 1A, within the range of λ. max The wavelengths with cross-transmittance Tc values ​​less than 1.0% in the absorption band of the maximum absorption wavelength are the longest wavelength side (λ1) and the shortest wavelength side (λ2).

[0368] [Table 1]

[0369]

[0370] As shown in Table 1A, Comparative Example 1A exhibits a Tc less than 1.0% in the wavelength range of 597 nm to 694 nm, but has a relatively narrow wavelength range with sufficient absorption. In contrast, Reference Example 1A has a Tc less than 1.0% in the wavelength range of 638 nm to 760 nm, and Reference Example 2A has a Tc less than 1.0% in the wavelength range of 637 nm to 761 nm, exhibiting sufficient absorption over a wide wavelength range.

[0371] Furthermore, Comparative Example 1A does not exhibit sufficient absorption at a wavelength of 730 nm because its Tc value is greater than 1.0% on the wavelength side longer than 694 nm. In contrast, Reference Examples 1A and 2A exhibit sufficient absorption at a wavelength of 730 nm because the wavelength range in which Tc is less than 1.0% includes 730 nm. Therefore, Reference Examples 1A and 2A are shown to be preferred compounds for providing polarizing films and the like with excellent orthogonal transmittance at a wavelength of 730 nm.

[0372] Table 1B shows the monomer transmittance Ts = 44.0% ± 0.1% for each test sample prepared in Reference Examples 1B to 2B and Comparative Example 1B, within the range of λ. max The wavelengths with cross-transmittance Tc values ​​less than 1.0% in the absorption band of the maximum absorption wavelength are the longest wavelength side (λ1) and the shortest wavelength side (λ2).

[0373] [Table 2]

[0374]

[0375] As shown in Table 1B, λ is relative to Comparative Example 1B. max The wavelength is 581 nm, and the λ value in Reference Example 1B is... max λ is 629nm, as in Reference Example 2B max It has λ at 628nm and at longer wavelengths. max When multiple dyes are mixed to fabricate a polarizing film, high optical properties are exhibited when the gaps in the absorption waveforms of each dye are filled. As shown in Tables 1A and 1B, since λ2 of Comparative Example 1A is 597 nm and λ1 of Comparative Example 1B is 617 nm, the gaps in the absorption waveforms can be filled by combining the azo compounds used in Comparative Examples 1A and 1B. However, in these combinations, it is not possible to fabricate a polarizing plate with sufficient polarization performance at 730 nm. Furthermore, since λ2 of Reference Example 1A is 638 nm, λ2 of Reference Example 2A is 637 nm, and λ1 of Comparative Example 1B is 617 nm, it is difficult to fill the gaps in the absorption waveforms of the azo compounds even when the azo compound used in Comparative Example 1B is combined with the azo compound used in Reference Examples 1A or 2A. In contrast, since λ1 is 667 nm in Reference Example 1B and 666 nm in Reference Example 2B, when the azo compound used in Reference Example 1B is combined with the azo compound used in Reference Example 1A or 2A, the gaps between the absorption waveforms can be filled, and a polarizing film with higher optical properties can be provided. Therefore, the combination of azo compounds represented by the above formulas (1) and (2) is preferred.

[0376] Table 1 shows the results of various transmittance and polarization properties of the test samples prepared in Examples 1 to 4 and Comparative Examples 1 to 9 in the wavelength range of 400 to 700 nm after visual sensitivity correction.

[0377] [Table 3]

[0378]

[0379] Compared to any of the polarizers in Comparative Examples 1 to 9, the polarizers of this application in Examples 1 to 4 shown in Table 1 exhibit high performance. Specifically, for Comparative Examples 1 to 5 with 4-color mixing (mixed with 4 compounds) and Comparative Examples 6 to 9 with 3-color mixing (mixed with 3 compounds), in either case, the embodiments of this application exhibit high contrast in the wavelength range of 400 to 700 nm.

[0380] Table 2 shows the results of various transmittance and polarization properties of the test samples prepared in Examples 1 to 4 and Comparative Examples 10 and 11 in the wavelength range of 380 nm to 780 nm after visual sensitivity correction.

[0381] [Table 4]

[0382]

[0383] As can be seen from Table 2, the polarizing plates of this application in Examples 1 to 4 exhibit high performance compared to any of the polarizing plates in Comparative Examples 10 and 11. Specifically, regarding Comparative Examples 10 and 11, which compare the three-color mixing in the wavelength range of 380 to 780 nm, each embodiment of this application exhibits high contrast in both cases.

[0384] When comparing the contrast of Examples 1 to 4, it was found that the values ​​shown in Table 2 were approximately 1,000 to 4,000 lower than those in Table 1. This is because, as shown in calculations (1) to (10), this result was affected by the visual sensitivity correction range. Furthermore, it is believed that when visual sensitivity correction was performed on Comparative Examples 1 to 9 in the range of 380 to 780 nm, the contrast also decreased.

[0385] Table 3 shows the polarization performance of each test sample in Examples 1 to 4 and Comparative Examples 12 and 13 under the condition that the visual sensitivity-corrected monomer transmittance (Ys) is consistent in the range of 380 to 780 nm.

[0386] [Table 5]

[0387]

[0388] As can be seen from Table 3, the polarizing plates of this application in Examples 1 to 4 exhibit higher polarization performance compared to the polarizing plates of Comparative Examples 12 and 13.

[0389] In the comparative examples listed in Table 1, even when compared with Comparative Example 6, which has a Ys value close to that of each embodiment and also has the highest polarization and good contrast, it is evident that each embodiment possesses high contrast. In the comparative examples listed in Table 2, even when compared with Comparative Example 10, which has the highest polarization and also has good contrast, it is evident that each embodiment possesses high contrast. Even when compared with Comparative Examples 12 and 13, which were prepared with a monomer transmittance (Ys) adjusted to be almost identical to that of each embodiment after visual sensitivity correction, it is evident that each embodiment possesses high contrast.

[0390] Furthermore, by using compound A and compound B in combination, the cross-transmittance values ​​of the polarizers in Examples 1 to 4 above 700 nm, especially the cross-transmittance values ​​at 730 nm, are 0 to 4% or less, which are lower than those in Comparative Examples 12 and 13. Therefore, it can be seen that the polarization performance on the long wavelength side is improved.

[0391] That is, it can be clearly understood that the polarizing plate of each embodiment is a polarizing plate with polarization performance, especially with high polarization and high contrast in a wide range of 380nm to 780nm, and with almost no light leakage in the long wavelength region.

[0392] Furthermore, even after 500 hours at an ambient temperature of 105°C or after 500 hours at an ambient temperature of 85°C and a relative humidity of 85%, the polarizing plates of Examples 1 to 3 showed almost no decrease in contrast or polarization, indicating that they exhibited long-term durability even under high temperature and high humidity conditions (these observations are a consensus reached by three experts).

[0393] Industrial availability

[0394] This invention provides polarizing films, polarizing plates, and optical components with optical properties equal to or superior to those of the past. The polarizing films or polarizing plates of this invention can be used in display devices, or similar optical devices, in liquid crystal projectors, calculators, clocks, laptops, word processors, liquid crystal televisions, polarizing lenses, polarizing glasses, head-up displays, automotive navigation systems, organic light-emitting diode displays (OLEDs), and indoor and outdoor measuring instruments and displays. A display device equipped with the polarizing film or polarizing plate of this invention is one embodiment of this invention. Furthermore, as a particularly preferred application of the polarizing plate of this invention, a display device equipped with the polarizing film or polarizing plate of this invention not only provides high polarization, i.e., high contrast, in the visible light region, particularly in the wavelength region of 380 to 780 nm, but also provides high durability. This durability refers to providing a display device whose polarization and contrast do not decrease even in environments with an ambient temperature of 105°C or a relative humidity of 85%. As a particularly preferred application, it is suitable for use in automotive displays, LCD projectors, head-up displays, outdoor displays, and other fields that require not only high contrast but also heat resistance, resistance to damp heat, and light resistance.

Claims

1. A polarizing film, characterized in that, It contains a substrate, and the substrate contains an azo compound or a salt thereof (compound A) represented by formula (1) and an azo compound or a salt thereof (compound B) represented by formula (2). In equation (1), X 1 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 1 and R 1 To R 4 Each can independently represent any substituent, and m represents an integer from 1 to 3. In equation (2), X 2 Q represents an amino group optionally having a substituent, a phenylamino group optionally having a substituent, a naphthylamino group optionally having a substituent, a benzoylamino group optionally having a substituent, or a naphthotriazolyl group optionally having a substituent, Q 2 and R 5 To R 8 Each can independently represent any substituent, R 9 This represents a hydrogen atom or a methyl group, and n represents an integer from 1 to 3.

2. The polarizing film according to claim 1, wherein, In equation (1), R 1 To R 4 Each of these can be independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group containing a sulfonyl group. X 1 It is an unsubstituted amino group or having one or two C1-C4 alkyl or phenyl-substituted C1-C4 alkyl groups, or an unsubstituted amino group or having one or two substituents independently selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation and amino, of the form phenylamino, naphthylamino, benzoylamino, or naphthotriazolyl. Q 1 It can be a hydrogen atom, a chlorine atom, a hydroxyl group, a hydroxyl group with a protecting group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy group with a sulfonyl group, a nitro group, a carboxyl group, or a sulfonyl group. In equation (2), R 5 To R 8 Each of these can be independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group containing a sulfonyl group. X 2 It is an unsubstituted amino group or having one or two C1-C4 alkyl or phenyl-substituted C1-C4 alkyl groups, or an unsubstituted amino group or having one or two substituents independently selected from the group consisting of C1-C4 alkoxy, C1-C4 alkoxy with sulfonation, C1-C4 alkyl, carboxyl, hydroxyl, sulfonation and amino, of the form phenylamino, naphthylamino, benzoylamino, or naphthotriazolyl. Q 2 It can be a hydrogen atom, a chlorine atom, a hydroxyl group, a hydroxyl group with a protecting group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkoxy group with a sulfonyl group, a nitro group, a carboxyl group, or a sulfonyl group.

3. The polarizing film according to claim 1, wherein, The azo compound or its salt represented by formula (1) is an azo compound or its salt represented by formula (3) below, and the azo compound or its salt represented by formula (2) is an azo compound or its salt represented by formula (4) below. In equation (3), R 1 To R 4 Each of these can independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group with a sulfonyl group, where m represents an integer from 1 to 3. In equation (4), R 5 To R 8 Each of the following independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy group with a sulfonyl group, R 9 denoted by methyl, and n represents an integer from 1 to 3.

4. The polarizing film according to claim 1, wherein it contains one or more dichroic dyes other than compounds A and B.

5. The polarizing film according to claim 1, wherein, The substrate contains a polyvinyl alcohol-based resin.

6. A polarizing plate having a transparent protective film disposed on one or both sides of the polarizing film according to any one of claims 1 to 5.

7. A display device comprising the polarizing plate of claim 6.

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