WO2008059702A1

WO2008059702A1 - Process for purification of polycyclic compounds, process for production of polycyclic compounds, and uses of polycyclic compounds

Info

Publication number: WO2008059702A1
Application number: PCT/JP2007/070814
Authority: WO
Inventors: Shoichi Matsuda; Junzo Miyazaki
Original assignee: Nitto Denko Corporation
Priority date: 2006-11-15
Filing date: 2007-10-25
Publication date: 2008-05-22

Abstract

The invention provides a process for production of polycyclic compounds substantially free from impurities such as sulfuric acid. The process comprises the step of synthesizing a polycyclic compound having a -SO3M group through sulfonation, the step of mixing the obtained synthetic with an organic solvent in which SO42- or SO3- is soluble and in which the polycyclic compound is slightly soluble to prepare a dispersion, and the step of filtering the dispersion to separate the polycyclic compound. Examples of the polycyclic compounds include quinoxaline derivatives represented by the general formula(I).

Description

Specification

Methods for purifying polycyclic compounds, methods for producing polycyclic compounds, and uses of polycyclic compounds

Technical field

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.

Three

Background art

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. However, since 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. There is a problem when. Birefringent films are used in LCDs to solve these problems. A birefringent film is also called a retardation film or an optical compensation film.

Conventionally, as one of 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

Disclosure of the invention

[0003] 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.

Three

did. 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.

4 was found to be the cause of the deterioration of the coatability of the aqueous solution, and the present invention was completed.

[0004] 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.

[0005] The first means of the present invention includes an impurity containing at least one of SO ² and SO—.

4 3

-A mixture containing a polycyclic compound having a SO M group (where M represents a counter ion)

Three

A method for purifying the polycyclic compound from a product, wherein the mixture is so ² or so

4 3

_ Is dissolved and the polycyclic compound is mixed with a poorly soluble organic solvent to obtain a dispersion, and the dispersion is filtered to separate the polycyclic compound.

[0006] According to the purification method, SO ² _ and / or SO _ contained in the polycyclic compound is

4 3 It flows out as a filtrate together with an organic solvent, and as a result, a polycyclic compound can be separated as a residue. Therefore, in the present invention, 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.

[0007] In a preferred method for purifying a polycyclic compound of the present invention, the organic solvent is at least one selected from methanol, ethanol, isopropyl alcohol, other lower alcohols, and acetone.

[0008] In another preferred method for purifying a polycyclic compound of the present invention, the polycyclic compound includes a quinoxaline derivative represented by the following general formula (I).

[0009] [Chemical 1] In 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.

Furthermore, in another preferred method for purifying a polycyclic compound of the present invention, the polycyclic compound includes a quinoxaline derivative represented by the following general formula (一般).

[0011] [Chemical 2]

In the formula (Π), M represents a counter ion. m represents the number of substitutions (an integer of 1 to 6).

[0012] Another preferable method for purifying a polycyclic compound according to the present invention is that the polycyclic compound has a wavelength of 4

It is a compound having the maximum value of the light absorption spectrum at 00 nm to 800 nm.

In another preferable method for purifying a polycyclic compound of the present invention, the polycyclic compound includes a perylene derivative represented by the following general formula (IV) or general formula (IV).

[0014] [Chemical 3]

In formula (III) and formula (IV), M represents a counter ion. nl ~! ι4 represents a substituent (an integer of 0 to 4). However, nl ~! All powers of ι4 are not 0 at the same time.

[0015] In another preferable method for purifying a polycyclic compound of the present invention, the amount of residual impurities in the polycyclic compound after separation is 100 mg / g or less.

[0016] Further, 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). Synthesize

Three

A step, wherein the compound is dissolved in so ² or so- and the polycyclic compound is hardly soluble

4 3

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.

[0017] 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.

[0018] In another preferable method for producing a polycyclic compound of the present invention, the polycyclic compound contains a quinoxaline derivative represented by the general formula (I).

[0019] According to another preferred method for producing a polycyclic compound of the present invention, the polycyclic compound has a wavelength of 4

[0020] In another preferable method for producing a polycyclic compound of the present invention, the polycyclic compound is soluble in water.

[0021] Further, 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.

[0022] A preferred coating liquid of the present invention exhibits a nematic liquid crystal phase.

Other preferred coating solutions of the present invention are prepared with a pH of 4 to 10;

[0023] 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.

[0024] 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.

[0025] According to the method for purifying a polycyclic compound and the method for producing a polycyclic compound of the present invention, impurities can be easily removed, and a highly pure polycyclic compound can be obtained.

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.

BEST MODE FOR CARRYING OUT THE INVENTION

The method for purifying a polycyclic compound of the present invention includes at least one of SO ² and SO—

4 3

And a polycyclic compound having a SO M group (where M represents a counter ion)

Three

The polycyclic compound can be easily purified from a mixture containing

Hereinafter, the method for purifying the polycyclic compound of the present invention will be described together with the method for producing the polycyclic compound.

[0027] (Polycyclic compound)

The polycyclic compound to be treated by the method of the present invention is a polycyclic compound having a SO M group.

Three

If it is a compound, it will not specifically limit. Furthermore, this polycyclic compound comprises a SO M group and

Three

COOM groups may be included. However, 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. In addition, 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. Specifically, 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. In addition, 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.

[0028] Examples of the quinoxaline-based polycyclic compound include acenaphtho represented by the following general formula (I):

Examples include [1, 2, b] quinoxaline derivatives. In the formula (I), 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). However, 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.

[0029] [Chemical 4]

The 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,

3 2 3

CONH group, SM group, OM group, etc. can be exemplified (in each group, M is a counter ion)

2

Represents). Preferably, 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. In the general formula (I), 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.

[0031] Further, examples of the quinoxaline-based polycyclic compound include acetnaphtho [1,2-b] quinoxaline derivatives represented by the following general formula (II). In formula (Π), 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). Among the quinoxaline derivatives represented by the general formula (Π), 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.

[0032] [Chemical 5]

[0033] Examples of perylene-based polycyclic compounds include perylene-based derivatives represented by the following general formula (III) or general formula (IV). In formula (III) and formula (IV), nl ~! ι4 represents the number of substitutions (an integer from 0 to 4). However, nl ~! ι4 is all 0 at the same time nl ~! At least one of ι4 is an integer from! Preferably, 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). In general formula (III) or general formula (IV), nl ~! ι4 is preferably an integer of 0 to 2, more preferably an integer of 0 to 1.

[0034] [Chemical 6]

In addition, examples of perylene-based polycyclic compounds include perylene-based derivatives represented by the following general formula (V) or general formula (VI). In formula (V) and 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). In general formula (V) or general formula (VI), 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.

Three

The Such perylene-based polycyclic compounds exhibit good orientation when applied.

[0036] [Chemical 7]

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)

Three

The above polycyclic compound has a SO M group (sulfonic acid or a salt thereof) in the basic skeleton of the compound.

Three

You can gain the power by introducing. The SO M group is, for example, a sulfonation treatment.

Three

It can be introduced by reason.

Examples of methods for synthesizing quinoxaline-based polycyclic compounds include the following 1) and 2).

1) A method of synthesizing a quinoxaline derivative having an SO M group introduced by sulfonating an unsubstituted or substituted quinoxaline derivative with fuming sulfuric acid or the like.

Three

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. A method for synthesizing a quinoxaline derivative having an M group introduced therein.

Three

[0039] As a specific method of the above 1), for example, 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. Examples of the inorganic sulfonic acid include sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid. Obtaining a quinoxaline derivative (polycyclic compound) having a SO M group by this method

Three

I can do it. In formula (a), 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).

[0040] [Chemical 8]

In addition, as a specific method of the above 2), for example, 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. After sulfonation with an inorganic sulfonic acid or the like, the benzenediamine and acenaphthoquinone are condensed. Examples of 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. In formula (b), 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).

[Chemical 9]

[0043] 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. Can be obtained by synthesizing a perylene derivative.

Three

wear.

[0044] (Purification of polycyclic compound)

Among the compounds obtained by the above synthesis, impurities that can generate SO ² _ or SO-

4 3

Remains. Impurities that can generate so ² or so-

4 3

Sulfuric acid and salts thereof, inorganic sulfonic acid and the like.

Since these impurities are non-volatile, they remain in the synthesized product even when dried. The present inventors have found that a compound containing a large amount of impurities such as sulfuric acid in a polycyclic compound cannot form a good coating film even if it is applied in the form of a solution on a substrate. ing. The cause of this is not clear, but when it is made into a solution, so ² _ or so-

It is estimated that this is an obstacle to coating film formation.

In the present invention, in order to substantially and easily remove the impurities in the synthesized product, the synthesized product (the synthesized product contains impurities such as sulfuric acid and SO M group obtained after sulfonation treatment) in an organic solvent. A mixture containing a polycyclic compound having

Three

The polycyclic compound is purified by separation.

[0045] The organic solvent used in the purification is SO ^{2 —} or SO— (preferably SO ^{2 —} and SO

4 3 4 3

In any case, a solvent in which a polycyclic compound having a SO M group is hardly soluble is used. It is.

Here, SO ² _ or SO- dissolves when SO ² _ or SO-

4 3 4 3

Solubility power at 3 ° C is about 10g / 100g or more. Also has SO M group

Three

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.

Examples of the organic solvent 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. The reason why water is not used as the solvent is that the polycyclic compound has high solubility in water.

[0046] The above compound (impurities containing at least one of SO ² _ and SO- and SO M groups

And a polycyclic compound having 4 3 3) are mixed with the organic solvent. Liquid synthesized was mixed with the organic solvent, the solution so 4 ² or / and so- was dissolved, polycyclic

Three

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

Four

If there are many organic solvents necessary, the cost of the solvent increases and the amount of the polycyclic compound to be purified may slightly decrease (depending on the type of organic solvent and the structure of the polycyclic compound, Formula compounds may be slightly soluble in organic solvents). For these reasons, the organic solvent is preferably about 200 to 10,000 parts by mass with respect to 100 parts by mass of the composite.

[0047] After mixing with an organic solvent, the mixture is sufficiently stirred to promote dissolution of SO ² _ and the like.

Four

Next, the obtained dispersion is filtered. The filtration method is preferably natural filtration using gravity or reduced pressure filtration in which the lower surface of the filter medium is decompressed. However, pressure filtration and centrifugal filtration can be used as the filtration method.

As the filter medium, cellulosic filter paper widely used for natural filtration and the like can be used. However, other than the cellulose type, for example, a filter medium other than paper such as glass fiber type may be used. As the filter medium, for example, it is preferable to use a filter medium having a pore size of about 0.8 in. By using the filter medium, SO ² and the polycyclic compound can be reliably and in a relatively short time.

Four

Can be separated.

When filter paper is used as the filter medium, the type of filter paper (mainly fineness of the eyes) is preferably, for example, 5 types C or 6 types for quantitative analysis. However, the above 5 types C and 6 types are filter paper standards based on JIS P 3801.

[0048] 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

Four

To be taken out. Therefore, so ² etc. and polycyclic compounds can be easily separated. Said residue

Four

The polycyclic compound can be purified by drying.

If necessary, the residue may be mixed with the organic solvent again and filtration may be repeated. By repeating the step of mixing with an organic solvent and filtering several times, a polycyclic compound with higher purity can be obtained.

[0049] In the step of mixing in the organic solvent and filtering (that is, purification of the polycyclic compound), 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. By reducing the amount of residual impurities to the range of lOOmg 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.

Four

[0050] <Coating liquid containing polycyclic compound>

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.

That is, 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.

Yes

When water is used as the solvent, the electrical conductivity of the water is preferably 20 S / cm The following (lower limit straight (to 0 S / cm), more preferably (to 0 · 001 S / cm to 10 S / cm, particularly preferably 0.01 H 3/111 to 5 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.

[0051] In 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.

Moreover, when 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.

[0052] Furthermore, 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.

[0053] In addition, 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. As the surfactant, a nonionic surfactant is preferably used. 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.

Yes

The birefringent film or polarizing film of the present invention can be obtained by forming a composition containing the above polycyclic compound.

(Production method of birefringent film or polarizing film)

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,

(2) a step of preparing at least one surface force S, a hydrophilized base material;

(3) A step of applying and drying the solution prepared in the above step (1) on the surface of the base material prepared in the step (2) which has been subjected to a hydrophilic treatment.

By such a production method, a laminated film having at least a birefringent film or a polarizing film and a substrate can be obtained.

Note that the order in which 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.

[0055] 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.

[0056] Further, 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 °.

[0057] Further, 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 °. By setting the water contact angle of the substrate within the above range, a birefringent film exhibiting a high in-plane birefringence and having a small thickness variation can be obtained. In addition, by making the water contact angle of the base material within the above range, it has excellent polarization characteristics, In addition, a polarizing film having a small thickness variation can be obtained.

[0058] Any appropriate method may be adopted as the hydrophilic treatment. The hydrophilic treatment may be, for example, a dry treatment or a wet treatment. Examples of 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. It is. Examples of 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! /.

[0059] Preferably, the hydrophilization treatment is a corona treatment, a plasma treatment, an alkali treatment, or an anchor coat treatment. With the above hydrophilization 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.

[0060] 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.

[0061] The substrate on which the coating liquid is applied is used to uniformly cast the coating liquid. Any appropriate substrate can be selected. Examples of 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.

[0062] As the glass substrate, any appropriate one can be selected. Preferably, the glass substrate can be equivalent to a cell substrate used for a liquid crystal cell. Examples of 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. Examples of 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.

[0063] As 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. However, the light transmittance is a film thickness of 100 m, and the Y value is corrected for visibility based on the spectrum data measured with a spectrophotometer (product name “U-4100”, manufactured by Hitachi, Ltd.). Say. The haze value of the polymer film is preferably 3% or less, more preferably 1% or less. However, 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. Preferably, the polymer film is a film containing a thermoplastic resin. Examples of 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. The above 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.

[0064] In the present invention, it is preferable to use a polymer film containing a cellulose resin as the substrate. Such a substrate is excellent in wettability with respect to a polycyclic compound. . By applying the coating solution to the substrate, a birefringent film having a high in-plane birefringence and a small thickness variation can be obtained. By applying the coating liquid to the substrate, a polarizing film having excellent polarization characteristics and small thickness variation can be obtained.

[0065] Any appropriate cellulose-based resin can be adopted. 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. Examples of the cellulose organic acid ester include cenololose acetate, cenololose propionate, cenololose butyrate and the like. Examples of 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].

[0066] As the base material used in the present invention, a commercially available polymer film may be used as it is. Alternatively, 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.

[0067] The thickness of the substrate is preferably 20 μm to 100 μm. By making the thickness of the substrate within the above range, the handling property of the substrate is improved.

[0068] In the above step (3), as a method of applying the coating liquid to the surface of the substrate, a coating method using an appropriate coater can be adopted as appropriate. Examples of 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. By setting the coating speed within the above range, 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.

[0069] As a method of drying the coating liquid after coating, an appropriate method can be appropriately employed.

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.

[0070] After the steps (1) to (3), the following step (4) may be further performed.

(4) 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. Contacting a solution containing at least one compound salt selected from the group consisting of compound salts.

[0071] 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.

[0072] 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.

[0073] 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). Examples of 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. When these methods are employed, 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.

[0074] (Properties of birefringent film, etc.)

In the birefringent film of the present invention containing the above polycyclic compound, 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. However, “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).

[0075] 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 (上記). When a film is formed using a coating solution containing such a polycyclic compound, a transparent birefringent film that does not absorb or is small in the visible light region can be obtained.

[0076] The birefringent film can be formed thin because it can be formed by coating. further The birefringent film satisfies the relationship of refractive index ellipsoidal curve ≥ «1 2〉 1 ^ (1«〉 1 2〉 1 ^ or 1 «= 1 z〉 ny) and has a high in-plane relationship. Has a birefringence. For this reason, the birefringent film has a desired retardation value with a much thinner thickness than the conventional birefringent film. In the present specification, “nx = nz” includes not only the case where nx and nz are completely the same, but also the case where they are substantially the same. The case where nx and nz are substantially the same includes, for example, Rth [590] -10nm to;! Onm.

According to the estimation of the present inventors, 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.

Three

In the middle (in the coating solution), the formation of 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.

Three

The cyclic compound is considered to exhibit high orientation.

[0077] 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. In this specification, the in-plane retardation value (Re [λ]) refers to the in-plane retardation value at 23 ° C. and the wavelength λ (nm). Re [λ] can be obtained by the formula: Re [λ] = (ηχ−ny) Xd, where d (nm) is the thickness of the birefringent film.

[0078] 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. In this specification, the thickness direction retardation value (Rth [λ]) is the thickness direction retardation value at 23 ° C. and the wavelength λ (nm). Rth [] can be obtained by the formula: Rth [λ] = (nx−nz) Xd, where d (nm) is the thickness of the film. [0079] 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].

[0080] The in-plane birefringence (Δ n [590] = nx-ny) of the birefringent film of the present invention at a wavelength of 590 nm at 23 ° C is preferably 0.05 or more, more preferably 0.1 to 0.5, and particularly preferably 0.2 to 0.4. Note that Δ η [590] can be appropriately adjusted within the above range depending on the molecular structure of the polycyclic compound.

[0081] The thickness of the birefringent film is preferably 0.05 μm to 10 μm, more preferably 0.1 μm to 8 μm, and particularly preferably 0.1. μm to 6 μm. The birefringent film in the above thickness range has a retardation value useful for improving the display characteristics of a liquid crystal display device.

[0082] (Characteristics of polarizing film, etc.)

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. However, 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.

[0083] 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 (ΠΙ) 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 · Οδ ^ ιη˜; 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 λ / 4 plate for a liquid crystal display device, a λ / 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. In one embodiment, the birefringent film can be laminated with a polarizing film to form a polarizing plate. Hereinafter, this polarizing plate will be described.

[0085] 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. As the polarizing film, the polarizing film of the present invention containing the above polycyclic compound may be used! /, Or another polarizing film may be used. As said other polarizing film, 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.

[0087] As the adhesive layer, 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. Examples of 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. In addition, 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.

[0088] 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. For example, when the polarizing plate is used as an antireflection film, 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 °. When the polarizing plate is used as a viewing angle widening film, 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. In the present specification, “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. °.

[0089] 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.

Example

[0090] The present invention will be further described using the following examples and comparative examples. Note that the present invention is not limited to these examples. A part of each analysis method used in the examples is as follows.

(1) Measuring method of thickness:

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.

(2) Refractive index measurement method:

Measurement was performed at 23 ° C. using a product name “KOBRA21—ADH” manufactured by Oji Scientific Instruments. As the average refractive index, a value measured using an Abbe refractometer (manufactured by Atago Co., Ltd., product name “DR-M4”) was used. (3) Measuring method of single transmittance and degree of polarization:

Measurement was performed at 23 ° C using a spectrophotometer (Murakami Color Research Laboratory Co., Ltd., product name “DOT-3”). 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

Yes

Polarization degree is measured by measuring parallel transmittance (H) and orthogonal transmittance (H), and the formula: degree of polarization (%) =

0 90

{(H—H) / (H + H)} ^1/2 X 100. Parallel transmittance (H) is

0 90 0 90 0 This is the transmittance value of a parallel laminate produced by superposing two polarizing films to be measured so that their absorption axes are parallel to each other. The orthogonal transmittance (H)

90

This is a transmittance value of an orthogonal laminate produced by superposing two optical films so that their absorption axes are orthogonal to each other. Note that these transmittances are Y values obtained by correcting the visibility using the J1S Z 8701-1982 2-degree field of view (C light source).

[0091] [Synthesis Example 1]

To a reaction vessel equipped with a stirrer, 5 liters of glacial acetic acid and 490 g of purified acenaphthenequinone were added and stirred for 15 minutes under nitrogen publishing to obtain a acenaphthenequinone solution. Similarly, 7.5 liters of glacial acetic acid and 275 g of o-phenylenediamine were added to another reaction vessel equipped with a stirrer, and stirred for 15 minutes under nitrogen bubbling to obtain o-phenylenediamine solution. . Thereafter, the o-phenylenediamine solution was gradually added to the caseen quinone quinone solution over 1 hour with stirring under a nitrogen atmosphere, and then the reaction was continued for 3 hours. Ion exchange water was added to the resulting reaction solution, and then the precipitate was filtered to obtain a crude product containing caseenaft [1,2-b] quinoxaline. The crude product was purified by recrystallization from hot ice acetic acid.

[0092] Next, as shown in the following reaction route (c), 300 g of the above-mentioned caseenaft [1, 2 b] quinoxaline was added to 30% fuming sulfuric acid (2.1 liters) and stirred for 24 hours at room temperature. The mixture was heated to 125 ° C and stirred for 32 hours to be reacted. While maintaining the resulting solution at 40 ° C. to 50 ° C., 4.5 liters of ion exchange water was added for dilution, and the mixture was further stirred for 3 hours. The precipitate was filtered and recrystallized with sulfuric acid to synthesize acenaphtho [1,2-b] quinoxaline 2,5 disulfonic acid (hereinafter referred to as 2,5 disulfo QAN). [0093] [Chemical 10]

[0094] [Example 1 1]

2 g of the wet cake product of the synthesized product (2,5-disulfo-QAN containing residual sulfuric acid) obtained in Synthesis Example 1 above was put in 10 g of methanol and sufficiently stirred to obtain a dispersion. This dispersion was filtered under reduced pressure using filter paper (trade name “NO. 5C” manufactured by Advantech Co., Ltd.) to obtain a residue. This residue was again mixed with 10 g of methanol and subjected to the same filtration. The process of mixing and filtering 10 g of methanol was repeated a total of 4 times. The residue obtained by final filtration was taken out and vacuum-dried at 60 ° C for 6 hours to obtain a solid content.

[0095] [Example 1 2]

A solid was obtained in the same manner as in Example 1-1 except that 10 g of acetone was used instead of methanol.

[0096] [Comparative Example 1 1]

A solid was obtained in the same manner as in Example 1-1 except that 10 g of toluene was used instead of methanol.

[0097] [Comparative Example 1 2]

Filtration was performed in the same manner as in Example 1-1 except that 10 g of cyclohexane was used in place of methanol to obtain a solid.

[0098] [Comparative Example 1 3]

Wet cake product of the synthesized product (residual sulfuric acid-containing 2, 5—disulfo—QAN) obtained in Synthesis Example 1. 1. 3 kg of 48.7 liters of ion-exchanged water (electric conductivity: 0.1 l S / cm) and neutralized by adding 9.8 liters of a 5% by weight aqueous solution of sodium hydroxide. The obtained aqueous solution is put into a supply tank, and using a high pressure RO element test apparatus equipped with a reverse osmosis membrane filter (product name “NTR-7430 filter element” manufactured by Nitto Denko Corporation) Circulation filtration was performed while adding reverse osmosis water so that the liquid amount was constant. Then, the residual sulfuric acid or its sulfate was removed until the electrical conductivity of the waste liquid reached 13.6 S / cm to obtain a purified aqueous solution.

[0099] [Synthesis Example 2]

In the same manner as in Synthesis Example 1, caseenaft [1,2-b] quinoxaline was obtained.

Next, as shown in the following reaction route (d), 300 g of the above-mentioned caseenaft [1, 2-b] quinoxaline was added to 30% fuming sulfuric acid (2.1 liters) and stirred at room temperature for 48 hours. I let you. While maintaining the obtained solution at 40 ° C. to 50 ° C., 4.5 liters of ion exchange water was added for dilution, and the mixture was further stirred for 3 hours. The precipitate was filtered to synthesize acenaphtho [1,2-b] quinoxaline-2-sulfonic acid (hereinafter referred to as 2-sulfo-QAN).

[0100] [Chemical 11]

[Example 2-1]

2 g of the wet cake product of the synthesized product (2-sulfo-QAN containing residual sulfuric acid) obtained in Synthesis Example 2 above was placed in 10 g of methanol and sufficiently stirred to obtain a dispersion. In the same manner as in Example 1-1, the process of mixing and filtering 10 g of methanol was performed a total of 4 times to obtain a solid matter.

[0102] [Example 2—2]

A solid was obtained in the same manner as in Example 2-1, except that 10 g of acetone was used instead of methanol.

[0103] [Example 2-3]

Filtration was performed in the same manner as in Example 2-1 except that 10 g of isopropyl alcohol was used instead of methanol to obtain a solid.

[Comparative 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.

[0105] [Comparative Example 2-2]

Filtration was performed in the same manner as in Example 2-1 except that 10 g of cyclohexane was used instead of methanol to obtain a solid.

[0106] [Comparative Example 2-3]

Dissolve 500 g of the wet cake product (2-sulfo-QAN containing residual sulfuric acid) obtained in Synthesis Example 2 in 35.5 liters of ion-exchanged water (electric conductivity: 0 · 1 HS / cm). Furthermore, 3.5 liters of a 5% by mass aqueous solution of sodium hydroxide was added for neutralization. The obtained aqueous solution is put into a supply tank, and the amount of liquid is constant using a high pressure RO element testing device equipped with a reverse osmosis membrane filter (product name “NTR-7430 filter element” manufactured by Nitto Denko Corporation). Circulation filtration was performed while adding reverse osmosis water. Then, the residual sulfuric acid or its sulfate was removed until the electrical conductivity of the waste liquid reached 8.06 S / cm to obtain a purified aqueous solution.

[Synthesis Example 3]

<Sulfonation of dibenzimidazole derivative of perylenetetracarboxylic acid> In a reaction vessel equipped with a stirrer, 30% fuming sulfuric acid (0.5 liter) was placed and stirred at 35 ° C while dibenzoimidazole derivative of perylenetetracarboxylic acid ( (Hereinafter referred to as PCDI) lOOg was gradually added to effect sulfonation. Thereafter, 4.5 liters of ion-exchanged water was diluted by dilution, and the reaction was terminated. The precipitate was filtered and recrystallized with sulfuric acid to obtain a PCDI sulfonate (see reaction formula (e)).

The PCDI used was a mixture of cis and transformer types as shown in equation (e).

A 0.1 mmol / L aqueous solution of this PCDI sulfonated product was prepared, and a light absorption spectrum was measured using a spectrophotometer (product name “U-4100 spectrophotometer” manufactured by Hitachi, Ltd.). Maximum absorption was shown.

[0108] [Chemical 12]

[Example 3— 1]

2 g of a wet cake product of the synthesized product (PCDI sulfonated product containing residual sulfuric acid) obtained in Synthesis Example 3 was placed in 10 g of methanol and sufficiently stirred to obtain a dispersion. This dispersion was filtered under reduced pressure using a filter paper (trade name “NO. 5C” manufactured by Advantech Co., Ltd.) to obtain a residue. This residue was again mixed with 10 g of methanol and subjected to the same vacuum filtration. The process of mixing and filtering 10 g of methanol was repeated a total of 4 times. The residue obtained by final filtration was taken out and vacuum-dried at 60 ° C. for 6 hours to obtain a final solid content.

[0110] [Example 3-2]

A solid was obtained in the same manner as in Example 3-1, except that 10 g of acetone was used instead of methanol.

[0111] [Example 3-3]

Filtration was performed in the same manner as in Example 3-1 except that 10 g of isopropyl alcohol was used instead of methanol to obtain a solid.

[0112] [Comparative Example 3-1]

A solid was obtained in the same manner as in Example 3-1, except that 10 g of toluene was used instead of methanol.

[0113] [Comparative Example 3-2]

Filtration was performed in the same manner as in Example 3-1 except that 10 g of cyclohexane was used instead of methanol to obtain a solid.

[0114] In order to evaluate the amount of sulfuric acid remaining in the solids of Example 1 1 3-3 and Comparative Example 1 1 3-2! It was. [0115] (Neutralization titration)

Evaluation of the residual sulfuric acid amount by neutralization titration is as follows. The solids of Example 1 above;! To 3-3 and Comparative Example 1 3-2 were dissolved in ion-exchanged water to prepare 0.1 mass% aqueous solutions. A 0.1% by mass aqueous solution of sodium hydroxide was added to 75 g of this aqueous solution, and neutralization titration was performed so that pH = 7.

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)) Χ 98 · 03} / 2] X (1000 / raw material solids (g)).

However, for Comparative Examples 1-3 and 2-3, neutralized titration could not be performed because a neutralized purified aqueous solution was obtained.

For reference, the residual sulfuric acid content of the synthesized products (before filtration treatment) synthesized in Synthesis Examples 1 to 3 was also measured in the same manner as described above.

[0116] (Electrical conductivity)

The electrical conductivity (S / cm) was measured using a solution conductivity meter (product name “CM-117” manufactured by Kyoto Electronics Industry Co., Ltd.). An aqueous solution for measurement was prepared as follows. Example 1 1;! To 3-3 and Comparative Example 1 1 3 2 were dissolved in ion-exchanged water to prepare a 0.1 mass% aqueous solution. An aqueous solution for measurement was obtained by adding a 0.1% by mass aqueous sodium hydroxide solution to this aqueous solution and neutralizing it to give a force of pH = 7.

Further, for Comparative Examples 13 and 2-3, 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. For reference, 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.

[0117] Table 1 shows the measurement results of the amount of residual sulfuric acid and electrical conductivity. As shown in Table 1, Example 1 one;

The solid matter of 3-3 had an extremely small amount of residual sulfuric acid compared to before treatment. Therefore, the method of Example 1 1 ;! to 3-3 could purify a highly pure polycyclic compound.

[0118] [Table 1] Residual sulfuric acid amount (mg) Electrical conductivity Polycyclic compound Separation method Organic solvent

Raw material solids (g) (μS / cm) Before treatment 2,5-disulfo-QAN ― ― 331.8 832 Example 1 1 1 2,5-disulfo-QAN Filtration Methanol 6.6 378 Example 1 1 2 2 1,5-disulfo-QAN filter Ji Acetone 386 386 Comparative example 1—1, 2,5-disulfo-QAN filter i§ Toluene 328.9 829 Comparative example 1 1 2 2,5-disulfo-QAN filtration Cyclohexane 330.4 831 Comparative example 1 _3 2,5-disulfo-QAN membrane--462 Before treatment 2-sulfo-QAN--382.7 794 Example 2— 1 2-sulfo-QAN filtration Methanol 14.1 250 Example 2— 2 2-sulfo-QAN filtration Acetone 1 7.7 255 Example 2-3 2-sulfo-QAN filter id IPA 1 5.9 252 Comparative example 2— 1 2-sulfo-QAN filtration Toluene 382.4 793 Comparative example 2— 2 2-sulfo-QAN filter Cyclohexane 380.8 792 Comparative example 2- 3 2-sulfo-QAN membrane ― ― 277 Before treatment PCDI sulfonated one ― 463.2 1 048 Example 3-1 PGDI sulfonated product Filtration methanol 9.4 232 Example 3-2 PCD1 sulfonated product in acetone 5.7 229 Example 3-3 PCDI sulfonated products @ IPA 8.2 284 Comparative Example 3-1 PCDI Sulfonated Filtration Toluene 457.4 903 Comparative Example 3-2 PCD1 Sulfonated Filtration Cyclohexane 461.99 954 [Example 4]

1 · 56 g of the solid material obtained in Example 1-2 and 0.84 g of the solid material obtained in Example 2-2 were mixed with 50 milliliters of ion-exchanged water (electric conductivity: 1.7 S / cm). Then, ammonium hydroxide was further added to neutralize so that ρΗ = 6 · 9. The obtained aqueous solution was prepared using a rotary evaporator so that the concentration of the polycyclic compound in the aqueous solution was 24% by mass. When the aqueous solution obtained here was observed with a polarizing microscope, it showed a nematic liquid crystal phase at 23 ° C.

Next, the above 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.

In the coating film formed in this way, the refractive index ellipsoid satisfies the relationship iix>nz> ny, and this can be used as a birefringent film. The coating film has a thickness of 0.6 um, Re [590] = 203 stomachs, Nz coefficient = 0 · 25.

[0120] [Comparative Example 4]

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.

When the surface of the obtained coating film was visually observed, many circular scuff marks having a diameter of 0.5 mm or more were generated.

[0121] [Example 5]

2 g of the solid material (PCDI sulfonated product) obtained in Example 3-2 was dissolved in 50 ml of ion-exchanged water (electric conductivity: 1.7 S / cm), and further 5% by mass. Was added to neutralize to pH = 4.58. 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. When the obtained aqueous solution was observed with a polarizing microscope, it exhibited a nematic liquid crystal phase at 23 ° C.

Next, place the above aqueous solution on a glass plate (Matsunami Glass Industry Co., Ltd., trade name “MATSUNAMI S LIDE GLASS”) with a thickness of 1 to 3 mm. It was applied 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 coating film thus formed can be used as a polarizing film. The coated film had a thickness of 0 · 35 111, a degree of polarization = 95%, and a single transmittance = 43%.

[0122] [Comparative Example 5]

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.

When the surface of the obtained coating film was visually observed, many circular cissing marks having a diameter of 0.3 mm or more were generated. Such a perforated membrane cannot be used as a film.

Claims

The scope of the claims

[1] A polycycle having an SO M group and an impurity containing at least one of SO ² and SO—

4 3 3

A mixture containing a compound of the formula (where M represents a counter ion), SO ² or SO—

4 3 Dissolving and mixing the polycyclic compound with a poorly soluble organic solvent to obtain a dispersion, and filtering the dispersion to separate the polycyclic compound. A method for purifying a polycyclic compound.

2. The method for purifying a polycyclic compound according to claim 1, wherein the organic solvent is at least one selected from methanol, ethanol, isopropyl alcohol, other lower alcohols, and acetone.

[3] The polycyclic compound comprises a quinoxaline derivative represented by the following general formula (I):

A method for purifying the polycyclic compound according to 1 or 2.

[Chemical 1]

In 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.

4. The method for purifying a polycyclic compound according to claim 3, wherein the polycyclic compound contains a quinoxaline derivative represented by the following general formula (Π).

[Chemical 2]

In the formula (Π), 表す represents a counter ion. m represents the number of substitutions (an integer of 1 to 6).

5. The method for purifying a polycyclic compound according to claim 1 or 2, wherein the polycyclic compound has a maximum value of a light absorption spectrum at a wavelength of 400 nm to 800 nm.

6. The method for purifying a polycyclic compound according to claim 5, wherein the polycyclic compound contains a perylene derivative represented by the following general formula (III) or general formula (IV).

[Chemical 3]

7. The method for purifying a polycyclic compound according to any one of claims 1 to 6, wherein the amount of residual impurities in the polycyclic compound after separation is 100 mg / g or less.

[8] A polycyclic compound having a sulfonation treatment and a SO M group (where M is a counter ion)

Three

A process for obtaining a composite by

The compound is an organic compound in which so ² or so- is dissolved and the polycyclic compound is hardly soluble.

4 3

Mixing with a solvent to obtain a dispersion,

Separating the polycyclic compound having a SO M group by filtering the dispersion;

Three

The manufacturing method of the polycyclic compound which has this.

9. The method for producing a polycyclic compound according to claim 8, wherein at least one selected from sulfuric acid, fuming sulfuric acid, and inorganic sulfonic acid is used as the sulfonation treatment.

[10] The polycyclic compound comprises a quinoxaline derivative represented by the following general formula (I): A process for producing the polycyclic compound according to 8 or 9.

[Chemical 4]

11. The method for producing a polycyclic compound according to claim 8 or 9, wherein the polycyclic compound has a maximum value of a light absorption spectrum at a wavelength of 400 nm to 800 nm.

[12] The method for producing a polycyclic compound according to any one of [8] to [11], wherein the polycyclic compound is soluble in water.

[13] A liquid obtained by dissolving, in water, the polycyclic compound separated by the purification method according to any one of claims 1 to 4 or the production method according to any one of claims 8 to; A coating solution showing a crystal phase.

[14] A coating solution showing a liquid crystal phase obtained by dissolving a polycyclic compound separated by the purification method according to claim 5 or 6 or the production method according to claim 11 in water.

[15] The coating liquid according to claim 13 or 14, which is a nematic liquid crystal phase.

[16] The coating solution according to claims 13 to 15, wherein the pH is adjusted to 4 to 10;

[17] A birefringent film satisfying a relationship of nx≥nz> ny obtained by coating the coating liquid according to claim 13 on a substrate and drying.

[18] A polarizing film obtained by coating the coating liquid according to claim 14 on a substrate and drying the coating liquid.