WO2008059702A1 - Procédé de purification de composés polycycliques, procédé de fabrication de composés polycycliques et utilisation de composés polycycliques - Google Patents

Procédé de purification de composés polycycliques, procédé de fabrication de composés polycycliques et utilisation de composés polycycliques Download PDF

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Publication number
WO2008059702A1
WO2008059702A1 PCT/JP2007/070814 JP2007070814W WO2008059702A1 WO 2008059702 A1 WO2008059702 A1 WO 2008059702A1 JP 2007070814 W JP2007070814 W JP 2007070814W WO 2008059702 A1 WO2008059702 A1 WO 2008059702A1
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polycyclic compound
polycyclic
film
integer
coating
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PCT/JP2007/070814
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English (en)
Japanese (ja)
Inventor
Shoichi Matsuda
Junzo Miyazaki
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Nitto Denko Corporation
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Priority claimed from JP2007182951A external-priority patent/JP5060853B2/ja
Application filed by Nitto Denko Corporation filed Critical Nitto Denko Corporation
Publication of WO2008059702A1 publication Critical patent/WO2008059702A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems

Definitions

  • the present invention relates to a method for purifying a polycyclic compound containing impurities such as sulfate ions, a method for producing a polycyclic compound having a SO M group, and uses thereof.
  • a liquid crystal display device (hereinafter sometimes referred to as “LCD”) is an element that displays characters and images by utilizing the electro-optical characteristics of liquid crystal molecules.
  • LCDs are widely used in mobile phones, notebook computers, liquid crystal televisions, and so on.
  • LCD uses liquid crystal molecules with optical anisotropy, even if it shows excellent display characteristics in one direction, the screen becomes dark or unclear in the other direction.
  • Birefringent films are used in LCDs to solve these problems.
  • a birefringent film is also called a retardation film or an optical compensation film.
  • birefringent films a film whose refractive index ellipsoid satisfies the relationship of nx> nz> ny is known (for example, see Patent Document 1).
  • This birefringent film is produced by a method in which a shrinkable film is attached to both sides of a polymer film, and the polymer film is stretched so as to expand in the thickness direction by shrinkage of the shrinkable film. For this reason, the birefringent film obtained cannot easily meet the demand for thinning and weight reduction that tends to be thick.
  • Patent Document 1 Japanese Patent Publication 2006-072309
  • the present inventors have studied various materials in order to obtain a thin and light birefringent film, and found that a polycyclic compound having a SOM group is a preferable material.
  • a birefringent film satisfying the relationship of nx ⁇ nz> ny can be obtained by dissolving such a polycyclic compound in water and coating the aqueous solution on a substrate. Based on this knowledge, we were further studying film formation using polycyclic compounds. In some cases, the aqueous solution of the polycyclic compound may not be applied uniformly. The present inventors have further conducted intensive studies on the cause, in an aqueous solution of a polycyclic compound so 2 _ etc.
  • An object of the present invention is to provide a method for purifying a polycyclic compound that can easily and substantially remove impurities such as sulfuric acid from the polycyclic compound.
  • Another object of the present invention is to provide a method for producing a polycyclic compound substantially free of impurities such as sulfuric acid.
  • Another object of the present invention is to provide a coating solution that contains the polycyclic compound and can be satisfactorily coated on a substrate.
  • the first means of the present invention includes an impurity containing at least one of SO 2 and SO—.
  • the force S can be used to separate and purify polycyclic compounds by a relatively simple method of filtration.
  • the purified polycyclic compound is prepared, for example, as a coating solution.
  • the coating liquid can be satisfactorily coated on the substrate, and as a result, a film having a substantially uniform thickness can be produced.
  • the organic solvent is at least one selected from methanol, ethanol, isopropyl alcohol, other lower alcohols, and acetone.
  • the polycyclic compound includes a quinoxaline derivative represented by the following general formula (I).
  • M represents a counter ion.
  • a and B represent substituents, and a and b represent the number of substitutions (a is an integer from 0 to 4, and b is an integer from 0 to 6).
  • 1 and m represent the number of substitutions (1 is an integer from 0 to 4, and m is an integer from 0 to 6). However, 1 and m are not 0 at the same time.
  • the polycyclic compound includes a quinoxaline derivative represented by the following general formula ( ⁇ ).
  • M represents a counter ion.
  • m represents the number of substitutions (an integer of 1 to 6)
  • Another preferable method for purifying a polycyclic compound according to the present invention is that the polycyclic compound has a wavelength of 4
  • the polycyclic compound includes a perylene derivative represented by the following general formula (IV) or general formula (IV).
  • M represents a counter ion.
  • nl ⁇ ! ⁇ 4 represents a substituent (an integer of 0 to 4). However, nl ⁇ ! All powers of ⁇ 4 are not 0 at the same time.
  • the amount of residual impurities in the polycyclic compound after separation is 100 mg / g or less.
  • the second means of the present invention relates to a method for producing a polycyclic compound, which is a sulfonating polycyclic compound having a SO M group (where M represents a counter ion).
  • It has a step of obtaining a dispersion by mixing with an organic solvent, and a step of filtering the dispersion to separate a polycyclic compound.
  • a preferred method for producing a polycyclic compound according to the present invention is to use sulfuric acid as the sulfonation treatment.
  • At least one selected from fuming sulfuric acid and inorganic sulfonic acid is used.
  • the polycyclic compound contains a quinoxaline derivative represented by the general formula (I).
  • the polycyclic compound has a wavelength of 4
  • the polycyclic compound is soluble in water.
  • the third means of the present invention relates to a coating solution, and the coating solution contains, in water, the polycyclic compound separated by any one of the above purification methods or any one of the production methods. It is obtained by dissolving.
  • a preferred coating liquid of the present invention exhibits a nematic liquid crystal phase.
  • a fourth means of the present invention relates to a birefringent film, and the birefringent film is obtained by applying any one of the above-mentioned coating liquids onto a substrate and drying, and has a refractive index.
  • the ellipsoid is characterized by satisfying the relationship nx ⁇ nz> ny.
  • a fifth means of the present invention relates to a polarizing film, and this polarizing film is obtained by applying any one of the above-mentioned coating solutions onto a substrate and drying.
  • the polycyclic compound obtained by such a method can be used as a solution to obtain a coating solution that can be satisfactorily applied to a substrate.
  • a film obtained by coating and drying this coating liquid on a substrate can be used as a birefringent film or a polarizing film.
  • the method for purifying a polycyclic compound of the present invention includes at least one of SO 2 and SO—
  • the polycyclic compound can be easily purified from a mixture containing
  • the polycyclic compound to be treated by the method of the present invention is a polycyclic compound having a SO M group.
  • this polycyclic compound comprises a SO M group and
  • COOM groups may be included.
  • M represents a counter ion (hereinafter the same).
  • the polycyclic compound to be treated by the method of the present invention may be one kind or two or more kinds having different structures.
  • the basic skeleton of the polycyclic compound is preferably two or more aromatic rings and / or heterocyclic rings More preferably 3 to 8 aromatic rings and / or heterocyclic rings.
  • the basic skeleton of the polycyclic compound preferably has at least a heterocyclic ring, and the heterocyclic ring preferably contains a nitrogen atom, more preferably the force S.
  • examples of the basic skeleton of the polycyclic compound include quinoxaline derivatives and perylene derivatives. These polycyclic compounds are preferable because they exhibit a liquid crystal phase (that is, lyotropic liquid crystal) in a solution state.
  • this liquid crystal phase is preferably a nematic liquid crystal phase in terms of excellent orientation. This nematic liquid crystal phase includes supramolecules, and the formed body is in a nematic state.
  • the quinoxaline-based polycyclic compound is preferably used as a material for forming a birefringent film.
  • the perylene-based polycyclic compound can be preferably used as a material for forming a polarizing film.
  • Examples of the quinoxaline-based polycyclic compound include acenaphtho represented by the following general formula (I):
  • Examples include [1, 2, b] quinoxaline derivatives.
  • a and B represent substituents, and a and b represent the number of substitutions (a is an integer of 0 to 4, and b is an integer of 0 to 6).
  • 1 and m represent the number of substitutions (1 is an integer from 0 to 4, and m is an integer from 0 to 6).
  • at least one of 1 and m which is not 0 at the same time is 1 or more.
  • M in the general formula (I) represents a counter ion.
  • the M is preferably a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a metal ion, or a substituted or unsubstituted ammonium ion.
  • the metal ions include Ni 2+ , Fe 3+ , Cu 2+ , Ag + , Zn 2+ , Al 3+ , Pd 2+ , Cd 2+ , Sn 2+ , Co 2+ , Mn 2+ , Ce 3+ and the like can be exemplified.
  • substituents represented by A and B in formula (I) may be the same or different.
  • Substituents for A and B include halogen atoms, substituted or unsubstituted carbon numbers;! To 2 alkyl groups, substituted or unsubstituted alkoxy groups having 1 to 2 carbon atoms, OCOCH groups, NH groups, NHCs OCH group, —NO group, CF group, CN group, OCN group, SCN group, COOM group,
  • CONH group, SM group, OM group, etc. can be exemplified (in each group, M is a counter ion)
  • At least one of A and B is a COOM group (carboxylic acid or a salt thereof). Even if the polycyclic compound has the above substituents represented by A and B, it can be separated by the method of the present invention.
  • the substitution numbers a and b are preferably 0 to 2, and more preferably the substitution numbers a and b are 0 to 1.
  • the polycyclic compound of the general formula (I) in which A and B are unsubstituted or have a small number of substitutions shows good orientation when coated.
  • examples of the quinoxaline-based polycyclic compound include acetnaphtho [1,2-b] quinoxaline derivatives represented by the following general formula (II).
  • formula ( ⁇ ) m represents the number of substitutions (an integer of 1 to 6).
  • M in the general formula (II) is the same as that in the formula (I).
  • a quinoxaline derivative in which m is 1 or 2 can be separated and purified in high yield / yield by the method of the present invention.
  • Examples of perylene-based polycyclic compounds include perylene-based derivatives represented by the following general formula (III) or general formula (IV).
  • nl ⁇ ! ⁇ 4 represents the number of substitutions (an integer from 0 to 4). However, nl ⁇ ! ⁇ 4 is all 0 at the same time nl ⁇ ! At least one of ⁇ 4 is an integer from!
  • at least one of nl and n2 is a force S; M in the above formulas (III) and (IV) is the same as in formula (I).
  • nl ⁇ ! ⁇ 4 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1.
  • perylene-based polycyclic compounds include perylene-based derivatives represented by the following general formula (V) or general formula (VI).
  • nl and n2 represent the number of substitutions (an integer of 0 to 4). However, at least one of nl and n2 is an integer of 1 to 4.
  • M in the above formulas (V) and (VI) is the same as in formula (I).
  • nl and n2 are each preferably an integer of 1 or 2.
  • the polycyclic compound represented by the general formula (V) or (VI) has SO M groups at both ends in the long axis direction of the basic skeleton.
  • the Such perylene-based polycyclic compounds exhibit good orientation when applied.
  • the perylene-based polycyclic compounds represented by the above general formulas (III) to (VI) are compounds having the maximum value of the light absorption spectrum in the wavelength range of 400 nm to 8 OOnm. Such a polycyclic compound is particularly suitable as a material for forming a polarizing film. [0038] (Synthesis of polycyclic compound having one SO M group)
  • the above polycyclic compound has a SO M group (sulfonic acid or a salt thereof) in the basic skeleton of the compound.
  • the SO M group is, for example, a sulfonation treatment.
  • Examples of methods for synthesizing quinoxaline-based polycyclic compounds include the following 1) and 2).
  • 1,2-Benzenediamine having an unsubstituted or substituted group or / and acenaphthoquinone having an unsubstituted or substituted group are sulfonated with fuming sulfuric acid and the like, and then both compounds are condensed to form SO.
  • acenaphtho [1,2b] quinoxaline represented by the following reaction formula (a) or a substituted product thereof is sulfonated with an inorganic sulfonic acid or the like.
  • the inorganic sulfonic acid include sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid.
  • At least one of 1,2-benzenediamine represented by the following formula (b) or a substituted product thereof, or acenaphthoquinone or a substituted product thereof is used.
  • the benzenediamine and acenaphthoquinone are condensed.
  • the inorganic sulfonic acid include sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid.
  • Quinoxari having one SO M group by force method Derivatives (polycyclic compounds) can be obtained.
  • A, a, B, b, 1 and m are the same as in formula (I) (provided that 1 and m are not 0 at the same time).
  • the perylene-based polycyclic compound of the present invention includes, for example, a perylene derivative (for example, a dibenzimidazole derivative of perylene tetracarboxylic acid) sulfonated with fuming sulfuric acid and the like, and an SO M group is introduced.
  • a perylene derivative for example, a dibenzimidazole derivative of perylene tetracarboxylic acid
  • SO M group is introduced.
  • the synthesized product in order to substantially and easily remove the impurities in the synthesized product, contains impurities such as sulfuric acid and SO M group obtained after sulfonation treatment) in an organic solvent.
  • impurities such as sulfuric acid and SO M group obtained after sulfonation treatment
  • the polycyclic compound is purified by separation.
  • the organic solvent used in the purification is SO 2 — or SO— (preferably SO 2 — and SO
  • a solvent in which a polycyclic compound having a SO M group is hardly soluble is used. It is.
  • SO 2 _ or SO- dissolves when SO 2 _ or SO-
  • Solubility power at 3 ° C is about 10g / 100g or more. Also has SO M group
  • the term “poorly soluble polycyclic compound” means that the solubility of the polycyclic compound in an organic solvent at 23 ° C. is about 0.5 g / 100 g or less.
  • the organic solvent examples include lower alcohols such as methanol, ethanol and isopropyl alcohol (preferably lower alcohols having 1 to 4 carbon atoms); acetone and the like. Among these, it is preferable to use methanol or / and acetone. In the present invention, one or more selected from these organic solvents can be used in combination.
  • water is not used as the solvent is that the polycyclic compound has high solubility in water.
  • a dispersion in which the formula compound is dispersed is obtained.
  • the amount of the organic solvent is not particularly limited as long as it is a sufficient amount for the synthesized product. Furthermore, if the amount of organic solvent is too small, so 2 etc. may not be sufficiently dissolved. On the other hand
  • the organic solvent is preferably about 200 to 10,000 parts by mass with respect to 100 parts by mass of the composite.
  • the filtration method is preferably natural filtration using gravity or reduced pressure filtration in which the lower surface of the filter medium is decompressed.
  • pressure filtration and centrifugal filtration can be used as the filtration method.
  • filter medium cellulosic filter paper widely used for natural filtration and the like can be used.
  • a filter medium other than paper such as glass fiber type may be used.
  • the filter medium for example, it is preferable to use a filter medium having a pore size of about 0.8 in.
  • the type of filter paper (mainly fineness of the eyes) is preferably, for example, 5 types C or 6 types for quantitative analysis.
  • 5 types C and 6 types are filter paper standards based on JIS P 3801.
  • the dispersion is separated into a filtrate and a residue by filtration. SO 2 _ and the like dissolved in the organic solvent are removed as a filtrate.
  • Polycyclic compounds that are sparingly soluble in organic solvents are
  • the polycyclic compound can be purified by drying.
  • the residue may be mixed with the organic solvent again and filtration may be repeated.
  • a polycyclic compound with higher purity can be obtained.
  • the amount of residual impurities (amount of sulfuric acid, sulfate, etc.) in the polycyclic compound is It is preferable to carry out until 1 OOmg or less, more preferably 20mg or less.
  • SO 2 and the like in the coating liquid described later can be made extremely small, and a coating liquid excellent in coating property can be prepared.
  • the high purity / polycyclic compound obtained through the above production method or purification method can be used for an appropriate purpose.
  • the use of the purified polycyclic compound is preferably a coating solution for forming a birefringent film or a coating film for forming a polarizing film.
  • the coating liquid can be prepared by dissolving the high-purity polycyclic compound obtained as described above in an appropriate solvent.
  • the polycyclic compound is water-soluble. For this reason, water can be used as a solvent for preparing the coating liquid.
  • the electrical conductivity of the water is preferably 20 S / cm
  • a birefringent film having a high in-plane birefringence can be obtained by using a coating liquid having an electric conductivity of water in the above range, wherein the electric conductivity is determined by the method described in the following examples. Can be measured.
  • the coating solution one or more of the above polycyclic compounds or two or more of different structures are dissolved.
  • the concentration of the polycyclic compound in the coating solution is not particularly limited. However, since the polycyclic compound exhibits a stable nematic liquid crystal phase in the solution, the concentration of the polycyclic compound is preferably 5% by mass to 35% by mass, more preferably 5% by mass to 30% by mass. The nematic liquid crystal phase can be confirmed and identified by the optical pattern of the liquid crystal phase observed with a polarizing microscope.
  • the pH value of the coating solution is low, it is desirable to add an alkali to adjust the pH to about 4 to 10, and further to about pH 6 to 8.
  • an additive may be added to the coating liquid.
  • Additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, UV absorbers, flame retardants, colorants, antistatic agents, compatibilizers, crosslinking agents, thickeners, etc. It can be illustrated.
  • the addition amount of these additives is preferably more than 0 and 10 parts by mass or less with respect to 100 parts by mass of the coating liquid.
  • a surfactant is added to the coating solution!
  • the surfactant is used to improve the wettability and coating property of the polycyclic compound to the substrate surface.
  • a nonionic surfactant is preferably used as the surfactant.
  • the additive amount of the surfactant is preferably more than 0 and 5 parts by mass or less with respect to 100 parts by mass of the coating liquid.
  • the birefringent film or polarizing film of the present invention can be obtained by forming a composition containing the above polycyclic compound.
  • the birefringent film or polarizing film of the present invention can be produced, for example, by a production method including the following steps (1) to (3). (1) a step of preparing the coating liquid,
  • a laminated film having at least a birefringent film or a polarizing film and a substrate can be obtained.
  • step (1) and step (2) are performed is not particularly limited, and step (2) may be performed after step (1) is performed first, or step (2). After performing step (1), step (1) may be performed, or step (1) and step (2) may be performed in parallel.
  • the "coating liquid” used in the above step (1) is as described above in the section "Coating liquid containing a polycyclic compound”.
  • the “hydrophilic treatment” in the above step (2) refers to a treatment for reducing the water contact angle of the substrate.
  • the hydrophilization treatment is performed in order to improve the wettability and coatability of the substrate surface on which the polycyclic compound is coated.
  • the hydrophilization treatment is a treatment that lowers the contact angle of water at 23 ° C of the substrate, preferably 10% or more, and more preferably 15% to 80% lower than before the treatment. Particularly preferred is a treatment for reducing by 20% to 70%.
  • the reduction ratio (%) is determined by the equation: ⁇ (contact angle before treatment, contact angle after treatment) / contact angle before treatment ⁇ X100.
  • the contact angle was measured using a solid-liquid interface analyzer (product name “Drop Master300j” manufactured by Kyowa Interface Science Co., Ltd.) (droplet 0.51, static contact angle measurement after 5 seconds from dropping). Can be measured.
  • the hydrophilization treatment is a treatment for reducing the contact angle of water at 23 ° C of the substrate, preferably by 5 ° or more, more preferably 10 ° to 65 ° compared to before treatment.
  • This is a treatment for lowering, particularly preferably a treatment for lowering by 20 ° to 65 °.
  • the hydrophilization treatment is a treatment wherein the contact angle of water at 23 ° C of the substrate is preferably 5 ° to 60 °, more preferably 5 ° to 50 °. Particularly preferred is a treatment of 5 ° to 45 °.
  • the hydrophilic treatment may be, for example, a dry treatment or a wet treatment.
  • the dry treatment include discharge treatment such as corona treatment, plasma treatment, and glow discharge treatment; flame treatment; ozone treatment; ionizing active ray treatment such as UV ozone treatment, ultraviolet treatment, and electron beam treatment.
  • the wet treatment include ultrasonic treatment using a solvent such as water and acetone, alkali treatment, anchor coating treatment, and the like. These treatments may be performed singly or in combination of two or more! /.
  • the hydrophilization treatment is a corona treatment, a plasma treatment, an alkali treatment, or an anchor coat treatment.
  • a birefringent film or a polarizing film having high orientation and low thickness fluctuation can be obtained.
  • the conditions for the hydrophilization treatment (for example, treatment time and strength) can be appropriately adjusted as appropriate so that the water contact angle of the base material falls within the above range.
  • the corona treatment is typically a treatment for modifying the substrate surface by passing the substrate through corona discharge.
  • Corona discharge is generated by applying high frequency and high voltage between a grounded dielectric roll and an insulated electrode, causing the air between the electrodes to break down and become ionized.
  • the plasma treatment is typically a treatment for modifying the substrate surface by passing the substrate through the low temperature plasma.
  • Low-temperature plasma is generated when a glow discharge occurs in an inorganic gas such as a low-pressure inert gas, oxygen, or halogen gas, and part of gas molecules is ionized.
  • the above ultrasonic cleaning treatment is typically a treatment that removes contaminants on the surface of the substrate and improves the wettability of the substrate by immersing the substrate in water or an organic solvent and applying ultrasonic waves. It is.
  • the alkali treatment is typically a treatment for modifying the substrate surface by immersing the substrate in an alkali treatment solution in which a basic substance is dissolved in water or an organic solvent.
  • the anchor coating treatment is typically a treatment for applying an anchor coating agent to the surface of the base material.
  • the substrate on which the coating liquid is applied is used to uniformly cast the coating liquid.
  • Any appropriate substrate can be selected.
  • the substrate include a glass substrate, a quartz substrate, a polymer film, a plastic plate, a metal plate such as aluminum and iron, and ceramics.
  • Examples include a tas substrate and a silicon wafer.
  • the substrate is preferably a glass substrate or a polymer film.
  • the glass substrate any appropriate one can be selected.
  • the glass substrate can be equivalent to a cell substrate used for a liquid crystal cell.
  • the glass substrate include soda lime glass (blue plate glass) containing an alkali component, or low alkali borosilicate glass.
  • a commercial item may be used as it is for the glass substrate.
  • commercially available glass base materials include glass cord “1737” manufactured by Kojung Co., Ltd., glass code “AN635” manufactured by Asahi Glass Co., Ltd., and glass code “NA-35” manufactured by NH Techno Glass Co., Ltd.
  • the polymer film a film having excellent visible light transmittance and excellent transparency is preferably used.
  • the light transmittance of visible light in this polymer film is preferably 80% or more, more preferably 90% or more.
  • the light transmittance is a film thickness of 100 m
  • the Y value is corrected for visibility based on the spectrum data measured with a spectrophotometer (product name “U-4100”, manufactured by Hitachi, Ltd.).
  • the haze value of the polymer film is preferably 3% or less, more preferably 1% or less.
  • the haze value is a value measured according to JIS-K 7105.
  • the resin for forming the polymer film is not particularly limited, and any appropriate resin can be selected.
  • the polymer film is a film containing a thermoplastic resin.
  • the thermoplastic resin include olefin resin, cycloolefin resin, chlorinated resin, cellulose resin, styrene resin, polymethyl methacrylate, polybutyl acetate, vinylidene chloride resin, polyamide resin, and polyacetal resin. , Force-bonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyarylate resin, amidoimide resin, imide resin, etc. It is done.
  • thermoplastic resins can be used alone or in combination of two or more.
  • the thermoplastic resin may be subjected to any appropriate polymer modification.
  • examples of the polymer modification include copolymerization, crosslinking, molecular terminals, and stereoregularity.
  • a polymer film containing a cellulose resin as the substrate.
  • a substrate is excellent in wettability with respect to a polycyclic compound. .
  • a birefringent film having a high in-plane birefringence and a small thickness variation can be obtained.
  • a polarizing film having excellent polarization characteristics and small thickness variation can be obtained.
  • the cellulose-based resin is preferably a cellulose organic acid ester or a cellulose mixed organic acid ester substituted with one group at least one of acetyl group, propionyl group and butyl group. It is.
  • the cellulose organic acid ester include cenololose acetate, cenololose propionate, cenololose butyrate and the like.
  • the cellulose mixed organic acid ester include cellulose acetate propionate and cenorelose acetate butyrate.
  • the above-mentioned senorelose resin can be obtained, for example, by the method described in Japanese Patent Publication No. 2001_188128 [0040] to [0041].
  • a commercially available polymer film may be used as it is.
  • a film obtained by subjecting a commercially available polymer film to secondary treatment such as stretching and / or shrinking may be used! /.
  • Commercially available polymer films containing cellulosic resins include Fuji Photo Film Co., Ltd.'s Fujitac series (trade names “ZRF80S”, “TD80UF”, “TDY—80UL”), KONiki Minoltaput Co., Ltd.
  • An example of the product name “KC8UX2M” is available.
  • the thickness of the substrate is preferably 20 ⁇ m to 100 ⁇ m. By making the thickness of the substrate within the above range, the handling property of the substrate is improved.
  • a coating method using an appropriate coater can be adopted as appropriate.
  • the coater include a reverse mouth single coater, a forward rotation low roll coater, a gravure coater, a rod coater, a slot die coater, a slot orifice coater, a curtain coater, and a fountain coater. If the coating method uses the coater, a birefringent film or a polarizing film with small thickness variation can be obtained.
  • the coating speed of the coating solution is preferably 50 mm / second or more, more preferably More than 100mm / sec.
  • a shearing force suitable for orienting the polycyclic compound is applied to the coating solution. For this reason, a birefringent film having a high in-plane birefringence and a small thickness variation can be obtained. Further, by setting the coating speed within the above range, a polarizing film having excellent polarization characteristics and small thickness variation can be obtained.
  • Drying can be performed by, for example, an air circulation type thermostatic oven in which hot or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature control, a heated heat pipe roll, a heated metal It can be performed using a belt or the like.
  • the drying temperature is equal to or lower than the isotropic phase transition temperature of the coating liquid, and it is preferable to gradually raise the temperature from a low temperature to a high temperature.
  • the drying temperature is preferably 10 ° C to 80 ° C, more preferably 20 ° C to 60 ° C. By setting the temperature range, a birefringent film or a polarizing film having a small thickness variation can be obtained.
  • the drying time can be appropriately selected depending on the drying temperature and the type of solvent. However, in order to obtain a birefringent film or a polarizing film with small thickness variation, the drying time is, for example, 1 minute to 30 minutes, preferably 1 minute to 10 minutes.
  • step (4) may be further performed.
  • the birefringent film or polarizing film obtained in the above step (3) has an aluminum salt, a sodium salt, a lead salt, a chromium salt, a strontium salt, and two or more amino groups in the molecule.
  • the above step (4) is carried out in order to make the obtained birefringent film or polarizing film insoluble or hardly soluble in water.
  • the above compound salts include aluminum chloride, barium chloride, lead chloride, chromium chloride, strontium chloride, 4,4'-tetramethyldiaminodiphenylmethane hydrochloride, 2,2'-dipyridyl hydrochloride, 4,4'-dipyridyl hydrochloride And melamine hydrochloride, tetraaminobilimidine hydrochloride and the like. With such a compound salt, a birefringent film or a polarizing film excellent in water resistance can be obtained.
  • the concentration of the compound salt in the solution containing the compound salt is preferably 3% by mass to 40% by mass. More preferably, it is 5 to 30% by mass.
  • a birefringent film or a polarizing film excellent in durability can be obtained by contacting a solution containing a compound salt in the above concentration range.
  • any appropriate method may be adopted as a method of bringing the solution containing the above compound salt into contact with the birefringent film or polarizing film obtained in step (3).
  • the method include a method of applying a solution containing the above compound salt to the surface of the birefringent film or polarizing film, or a method of immersing the birefringent film or polarizing film in a solution containing the above compound salt. Is mentioned.
  • the obtained birefringent film or polarizing film is preferably washed with water or an arbitrary solvent. Thereafter, by further drying, a laminate having excellent interface adhesion between the substrate and the birefringent film or polarizing film can be obtained.
  • the refractive index ellipsoid satisfies the relationship of nx ⁇ nz> ny.
  • the birefringent film exhibits birefringence in the in-plane and / or thickness direction and in-plane and / or birefringence power of the thickness direction 1 X 10_ 4 or more at a wavelength of 590nm at 23 ° C.
  • nx ⁇ nz> ny represents the optical anisotropy of the birefringent film.
  • nx is the refractive index in the direction that maximizes the refractive index in the plane of the birefringent film (that is, the slow axis direction), and ny is the direction that is orthogonal to the slow axis direction in the plane (that is, the fast phase) Representing the refractive index in the axial direction, nz represents the refractive index in the thickness direction (hereinafter the same).
  • the polycyclic compound used as the material for forming the birefringent film of the present invention is preferably a compound having two or more aromatic rings and / or heterocyclic rings in the molecular structure, and more preferably. , A compound having 3 to 8 aromatic rings and / or heterocycles, particularly preferably a compound having 4 to 6 aromatic rings and / or heterocycles.
  • the material for forming the birefringent film is most preferably a polycyclic compound represented by the above general formula (I) or ( ⁇ ⁇ ).
  • the reason why the birefringent film of the present invention exhibits high birefringence is as follows. That is, the polycyclic compound containing the SO M group is a solution.
  • this aggregate which is easy to form an aggregate, is high in order, so the film formed from the force and the solution also shows high orientation and high birefringence. It is thought that a film can be formed. In particular, it has many SO M groups and COOM groups.
  • the cyclic compound is considered to exhibit high orientation.
  • the transmittance of the birefringent film at a wavelength of 590 nm is preferably 85% or more, and more preferably 90% or more.
  • the in-plane retardation value (Re [590]) of the birefringent film at a wavelength of 590 nm can be set to an appropriate value depending on the purpose.
  • the above Re [590] is 10 nm or more, preferably 20 to 1000, more preferably 50 to 500, and particularly preferably 100 to 400 nm.
  • the in-plane retardation value (Re [ ⁇ ]) refers to the in-plane retardation value at 23 ° C. and the wavelength ⁇ (nm).
  • Rth [590] of the birefringent film can be set to an appropriate value as long as the refractive index ellipsoid satisfies the relationship of nx ⁇ nz> ny.
  • the difference (Re [590] — Rth [590]) between the in-plane retardation value (Re [590]) and the thickness direction retardation value (Rth [590]) of the birefringent film at a wavelength of 590 nm is The thickness is preferably 10 nm to 800 nm, more preferably 10 nm to 400 nm, and particularly preferably 10 nm to 200 nm.
  • the thickness direction retardation value (Rth [ ⁇ ]) is the thickness direction retardation value at 23 ° C. and the wavelength ⁇ (nm).
  • the Nz coefficient of the birefringent film is preferably more than 0 and less than 1, more preferably (or 0.1 to 0.8, particularly preferably (or 0.1 to 0). 7, most preferably (0.1 to 0.6). If the Nz coefficient is in the above range, the birefringent film of the present invention can be used for optical compensation of liquid crystal cells in various drive modes. In this specification, the Nz coefficient is a value calculated from Rth [590] / Re [590].
  • the thickness of the birefringent film is preferably 0.05 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 8 ⁇ m, and particularly preferably 0.1. ⁇ m to 6 ⁇ m.
  • the birefringent film in the above thickness range has a retardation value useful for improving the display characteristics of a liquid crystal display device.
  • the polarizing film of the present invention containing the above polycyclic compound has a polarization degree of preferably 90% or more, more preferably 95% or more.
  • the single transmittance of the polarizing film is preferably 35% or more, more preferably 40% or more.
  • the single transmittance and degree of polarization are values based on a wavelength of 550 nm at 23 ° C. The reason why a polarizing finale having such a strong polarization property can be obtained is that the polycyclic compound exhibits high orientation by applying a coating solution.
  • the polycyclic compound used as the material for forming the polarizing film of the present invention is a compound having the maximum value of the light absorption spectrum in the wavelength range of 400 nm to 800 nm.
  • the polycyclic compound is preferably a compound having a maximum value of light absorption spectrum within a wavelength range of 400 nm to 800 nm and having two or more aromatic rings and / or heterocyclic rings in the molecular structure. More preferably a compound having the same maximum value and having 3 to 8 aromatic rings and / or heterocycles, and particularly preferably a polycyclic compound having a perylene skeleton.
  • the material for forming the polarizing film is most preferably a polycyclic compound represented by the above general formulas ( ⁇ ) to (VI). A film is formed using a coating solution containing such a polycyclic compound. Then, a polarizing film excellent in dichroism can be obtained.
  • the thickness of the polarizing film is preferably 0 ⁇ ⁇ ⁇ ⁇ ⁇ ; 10 ⁇ m, more preferably 0.1 111-5111. Since the polarizing film of the present invention can be formed by coating, it can be formed thin.
  • the use of the birefringent film of the present invention is not particularly limited, but is typically a ⁇ / 4 plate for a liquid crystal display device, a ⁇ / 2 plate and a viewing angle widening film; an antireflection film for a flat panel display, Etc. Power S is mentioned.
  • the birefringent film can also be used for image display devices such as organic EL display devices.
  • the birefringent film can be laminated with a polarizing film to form a polarizing plate.
  • this polarizing plate will be described.
  • the polarizing plate of the present invention comprises at least the birefringent film of the present invention and a polarizing film.
  • This polarizing plate may include a laminated film including at least the birefringent film of the present invention and a base material, or may include another birefringent film or an optional protective layer. Practically, an arbitrary appropriate adhesive layer is provided between the constituent layers of the polarizing plate, and the birefringent film and the constituent members are attached.
  • the polarizing film constituting the polarizing plate is not particularly limited as long as it has optical characteristics that convert natural light or polarized light into linearly polarized light.
  • the polarizing film of the present invention containing the above polycyclic compound may be used! /, Or another polarizing film may be used.
  • the stretched film which has as a main component the polybulal alcohol-type resin containing an iodine or a dichroic dye is preferable.
  • the thickness of the polarizing film composed of this stretched film is usually 5 am to 50 am.
  • any appropriate layer can be selected as long as it is a layer that joins surfaces of adjacent members and integrates them with practically sufficient adhesive force and adhesive time.
  • the material forming the adhesive layer include an adhesive, a pressure-sensitive adhesive, and an anchor coat agent.
  • the adhesive layer may have a multilayer structure in which an anchor coating agent is applied to the surface of the adherend and an adhesive or a pressure-sensitive adhesive is applied thereon.
  • the adhesive layer may not be recognized macroscopically! /, Such a thin layer! /, Or a layer (also known as a hairline)! /.
  • Above polarizing film The adhesive layer disposed on one side of the system and the adhesive layer disposed on the other side may be the same or different.
  • the angle at which the polarizing film and the birefringent film are attached to the polarizing plate can be appropriately set according to the purpose.
  • the angle between the absorption axis direction of the polarizing film and the slow axis direction of the birefringent film is preferably 25 ° to 65 °. More preferably 35 ° to 55 °.
  • the angle between the polarizing film absorption axis direction and the birefringent film slow axis direction of the polarizing plate is substantially parallel or substantially orthogonal. It is.
  • substantially parallel includes an angle between the absorption axis direction of the polarizing film and the slow axis direction of the birefringent film, and includes a range of 0 ° ⁇ 10 °, preferably 0 ° ⁇ 5 °.
  • substantially orthogonal includes the range of 90 ° ⁇ 10 °, preferably 90 ° ⁇ 5 °, which is the angle force between the absorption axis direction of the polarizing film and the slow axis direction of the birefringent film. °.
  • the application of the polarizing film of the present invention is not particularly limited, but is typically an optical application of a liquid crystal display device. Since the polarizing film of the present invention is formed by coating on a substrate, the substrate can also be used as a protective film.
  • a part of the coating film formed on the surface of the base material (glass plate) is peeled off, and the step between the base material and the coating film is measured with a three-dimensional non-contact surface shape measurement system (manufactured by Ryoka System Co., Ltd. measured using the name "Mi C ram a p MM5200"), which was the thickness.
  • the measured values of polarization degree and single transmittance were based on a wavelength of 550 nm.
  • the single transmittance is tristimulus Y ⁇ t based on the two-degree field of view of J1S Z 8701-1995
  • a solid was obtained in the same manner as in Example 1-1 except that 10 g of acetone was used instead of methanol.
  • a solid was obtained in the same manner as in Example 1-1 except that 10 g of toluene was used instead of methanol.
  • a solid was obtained in the same manner as in Example 2-1, except that 10 g of acetone was used instead of methanol.
  • Example 2-1 A solid was obtained in the same manner as in Example 2-1, except that 10 g of toluene was used instead of methanol.
  • the PCDI used was a mixture of cis and transformer types as shown in equation (e).
  • a solid was obtained in the same manner as in Example 3-1, except that 10 g of acetone was used instead of methanol.
  • a solid was obtained in the same manner as in Example 3-1, except that 10 g of toluene was used instead of methanol.
  • the amount of residual sulfuric acid was determined according to the following formula.
  • Residual sulfuric acid amount (mg) / raw material solid content (g) [ ⁇ (base amount in sodium hydroxide aqueous solution used for titration (mol)-assuming that all the raw material solid content used for titration is the target quinoxaline. Acid amount (mol)) ⁇ 98 ⁇ 03 ⁇ / 2] X (1000 / raw material solids (g)).
  • the electrical conductivity (S / cm) was measured using a solution conductivity meter (product name “CM-117” manufactured by Kyoto Electronics Industry Co., Ltd.).
  • the purified aqueous solution obtained was diluted by adding ion-exchanged water so as to have the same concentration as above to obtain an aqueous solution for measurement.
  • the electrical conductivity of the synthesized products (before filtration treatment) synthesized in Synthesis Examples 1 to 3 was also measured by the same method as described above.
  • Table 1 shows the measurement results of the amount of residual sulfuric acid and electrical conductivity. As shown in Table 1, Example 1 one;
  • aqueous solution is applied to a 1.3 mm thick glass plate (trade name “MATSUNAMI S LIDE GLASS” manufactured by Matsunami Glass Industrial Co., Ltd.) and a bar coater (trade name “m ayer rot HS 1.5” manufactured by BUSCHMAN). And dried in a constant temperature room at 23 ° C. When the surface of the coating film was visually observed, it was uniformly coated without repelling.
  • the refractive index ellipsoid satisfies the relationship iix>nz> ny, and this can be used as a birefringent film.
  • Example 3 Same as Example 3 except that 1.56 g of the compound obtained in Synthesis Example 1 (before filtration) and 0.84 g of the compound obtained in Synthesis Example 2 (before filtration) were used. An aqueous solution was prepared and applied to form a coating film on a glass plate.
  • the obtained aqueous solution was concentrated using a rotary evaporator until the concentration of the PCDI sulfonated product in the aqueous solution reached 11% by mass.
  • the obtained aqueous solution was observed with a polarizing microscope, it exhibited a nematic liquid crystal phase at 23 ° C.
  • the coating film thus formed can be used as a polarizing film.
  • An aqueous solution was prepared in the same manner as in Example 5 except that 2.0 g of the synthesized product obtained in Synthesis Example 3 (before filtration) was used, and this was coated to form a coating film on a glass plate. Formed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un procédé de fabrication de composés polycycliques sensiblement exempts d'impuretés tels que l'acide sulfurique. Le procédé comporte l'étape consistant à synthétiser un composé polycyclique ayant un groupe -SO3M par sulfonation ; l'étape consistant à mélanger le composé de synthèse obtenu avec un solvant organique dans lequel SO42- ou SO3- est soluble et dans lequel le composé polycyclique est légèrement soluble pour préparer une dispersion ; et l'étape consistant à filtrer la dispersion pour séparer le composé polycyclique. Des exemples des composés polycycliques comprennent les dérivés de la quinolaxine représentés par la formule générale (I).
PCT/JP2007/070814 2006-11-15 2007-10-25 Procédé de purification de composés polycycliques, procédé de fabrication de composés polycycliques et utilisation de composés polycycliques WO2008059702A1 (fr)

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JP2006-309194 2006-11-15
JP2006309194 2006-11-15
JP2007-182951 2007-07-12
JP2007182951A JP5060853B2 (ja) 2006-11-15 2007-07-12 多環式化合物の精製方法、多環式化合物の製造方法、及び多環式化合物の用途

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Publication number Priority date Publication date Assignee Title
JPH08511109A (ja) * 1993-05-21 1996-11-19 ロシアン テクノロジー グループ 熱安定で且つ耐光堅牢な二色偏光子
WO2004096805A2 (fr) * 2003-04-25 2004-11-11 Nitto Denko Corporation Systemes de cristaux liquides lyotropes a base de sulfoderives de dibenzimidazole d'acide perylenetetracarboxylique, films anisotropes apparentes, et leurs procedes de realisation
WO2005003132A1 (fr) * 2003-06-25 2005-01-13 Nitto Denko Corporation Sulfoderives dibenzimidazole d'acide perylenetetracarboxylique contenant des groupes oxo dans le noyau perylene qui font partie integrante d'un systeme para-quinoide de liaisons, systemes de cristaux liquides lyotropique et films anisotropiques contenant ces systemes, ainsi que methodes de fabrication de ceux-ci
WO2005051926A1 (fr) * 2003-11-21 2005-06-09 Nitto Denko Corporation Sulfoderives d'acenaphtho[1,2-b]quinoxaline, cristaux liquides lyotropes et film anisotrope a base desdits derives
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WO2007042788A2 (fr) * 2005-10-07 2007-04-19 Crysoptix Limited Compose organique, film a cristaux liquides optiques et procede de production associe

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JPH08511109A (ja) * 1993-05-21 1996-11-19 ロシアン テクノロジー グループ 熱安定で且つ耐光堅牢な二色偏光子
WO2004096805A2 (fr) * 2003-04-25 2004-11-11 Nitto Denko Corporation Systemes de cristaux liquides lyotropes a base de sulfoderives de dibenzimidazole d'acide perylenetetracarboxylique, films anisotropes apparentes, et leurs procedes de realisation
WO2005003132A1 (fr) * 2003-06-25 2005-01-13 Nitto Denko Corporation Sulfoderives dibenzimidazole d'acide perylenetetracarboxylique contenant des groupes oxo dans le noyau perylene qui font partie integrante d'un systeme para-quinoide de liaisons, systemes de cristaux liquides lyotropique et films anisotropiques contenant ces systemes, ainsi que methodes de fabrication de ceux-ci
WO2005051926A1 (fr) * 2003-11-21 2005-06-09 Nitto Denko Corporation Sulfoderives d'acenaphtho[1,2-b]quinoxaline, cristaux liquides lyotropes et film anisotrope a base desdits derives
JP2005352322A (ja) * 2004-06-11 2005-12-22 Dainippon Printing Co Ltd 偏光板、およびこれを用いた液晶表示素子用基板ならびに液晶表示素子
WO2007042788A2 (fr) * 2005-10-07 2007-04-19 Crysoptix Limited Compose organique, film a cristaux liquides optiques et procede de production associe

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