JP2010241981A - Compound for anisotropic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound for an anisotropic film having high dichroism in a short wavelength region and excellent durability. <P>SOLUTION: A free acid of the compound for the anisotropic film is represented by formula (1) (in formula, X<SP>1</SP>and X<SP>2</SP>each denotes an -N=N- group or an -NH-CO-(*) group, (*) denotes a bonding position to Y<SP>1</SP>or Y<SP>2</SP>, Y<SP>1</SP>and Y<SP>2</SP>each denotes an alkyl, an alkenyl, a phenyl or a naphthyl having at least one substituent of a sulfo, a carboxy, an -O(CH<SB>2</SB>)<SB>n</SB>CO<SB>2</SB>H or an -O(CH<SB>2</SB>)<SB>m</SB>SO<SB>3</SB>H, m and n each denotes an integer of 1 to 4, p and q each denotes 0 or 1, both p and q are 0 or 1, R<SP>1</SP>to R<SP>8</SP>each denotes an alkyl, an alkoxy, an OH, an amino, an acetylamino, a halogen atom or H). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is for anisotropic films useful for light-emitting display elements such as light control elements, liquid crystal elements (LCDs), and organic electroluminescence elements (OLEDs), and polarizing films provided in input / output elements such as touch panels. It relates to compounds.

  In recent years, flat displays such as LCDs have come to be widely used in television receivers, and are replacing conventional televisions using CRT. Further, the color reproducibility of NTSC, which is the current television system, is determined based on the characteristics of CRT phosphors, and there is a problem that only about half of the color of an actual object can be expressed. On the other hand, imaging devices such as digital cameras and camcorders have recently been able to express a wider range of colors (color reproduction) than the range defined by NTSC, and a display compatible with an extended color space that reproduces the information more accurately is desired. It is rare.

  In such a background, a flat display that replaces a CRT, such as an LCD, is a device capable of expressing a higher saturation color than a CRT in principle, and an extended color space for a new movie that takes advantage of the high functionality of the flat display. Standardization has been promoted. As a result, “Extended-gamut YCC color space for video application-xyYCC” has been issued as the international standard IEC 61966-2-4.

The xyYCC color space is a standard that can represent almost all of the actual object colors, and thereby, it is possible to express even the material feeling and stereoscopic effect of colorful objects.
However, when the extended color space information is to be displayed on a conventional LCD, the characteristics of various members used in the LCD are not sufficient, so there are some improvements to construct a display that supports the xyYCC color space. It is being advanced.

For example,
(1) Adoption of backlight with good color purity of the three primary colors RGB
(2) Use of a micro color filter in which complementary colors are added to the three primary colors RGB.
Typical means of (1) is the use of LEDs and optimization of the emission wavelength of the phosphor used in the cold cathode tube, and (2) is the use of micro color filters with yellow and cyan added ( (See Patent Documents 1 and 2).

As described above, the factors governing the color reproducibility of the LCD are members related to light emission and members having absorption in the visible light wavelength range, but a polarizing film having absorption in the visible light wavelength region as well as the micro color filter. With regard to (polarizing film), sufficient studies have not yet been made.
In order to cope with the xyYCC extended color space, it is necessary to improve the characteristics of the short wavelength region and the long wavelength region corresponding to both ends of the visible light, as estimated from the improvement contents of the backlight and the micro color filter.

  However, the conventional polarizing film has a problem that the contrast ratio at a specific wavelength or color is lowered because optical characteristics such as absorbance and dichroism in the visible light wavelength region are not constant. In particular, since the dichroism in the short wavelength region, which is a complementary color of blue light, is low, the color purity of blue light is lowered and color reproducibility may not be sufficiently obtained.

  In addition to displays that support extended color spaces, in the case of liquid crystal projectors and in-vehicle liquid crystal panels, organic compounds that have dichroism over the entire visible light wavelength region are used instead of iodine because of durability problems at high temperatures. It has been. However, a compound having absorption at a short wavelength tends to have a smaller π-conjugate spread, that is, a shorter molecular length than a compound having absorption at a long wavelength, as a general characteristic of the molecular structure. Usually, in order to obtain a sufficient aspect ratio in a dichroic compound, it is necessary to have a long molecular length. Therefore, when a compound having absorption at a short wavelength is used as a dichroic compound, It is difficult to achieve both. For this reason, the polarizing films that have been used so far have low dichroism in the short wavelength region, and here too, development of a compound having high dichroism in the short wavelength region has been desired. In addition, in these applications, because there is a problem that defects due to film shrinkage due to temperature and humidity changes called frame failure or frame unevenness, durability at high temperatures is required, Development of a novel dichroic compound is also desired because the combination of a polymer material such as modified polyvinyl alcohol (polyvinyl alcohol derivative) and a dichroic substance that solves this problem has become important.

As a dichroic compound that solves such a problem, for example, an azo compound having both a stilbene moiety and an alkenylamide or alkynylamide moiety has been proposed (see Patent Document 3). These compounds were thought to be excellent in molecular linearity and dichroic ratio, but there was still room for improvement in order to obtain a practically sufficient dichroic ratio.
For example, as a method of further improving the dichroic ratio, a method of increasing the aspect ratio by increasing the molecular length and improving the dichroism can be considered, but in the conventional method, the composition for anisotropic film is used. It was difficult to impart sufficient water solubility to the compound. In order to further improve the practicality, it is necessary to improve the color tone by introducing substituents. However, the conventional methods limit the types and positions of substituents that can be introduced to impart water solubility to the compound. It was difficult to achieve high dichroism.

JP 2007-73290 A JP 2007-25285 A International Publication No. 2009/8298 Pamphlet

An object of the present invention is to provide a compound for an anisotropic film which is useful for a polarizing film capable of expressing a wide range of colors and has absorption mainly in a short wavelength region.
Moreover, this invention makes it a subject to provide the compound for anisotropic films excellent in durability.

  As a result of intensive studies by the present inventors, it has been found that a compound for anisotropic film, in which the form of the free acid is represented by the following formula (1), can solve the above problems, and the present invention has been achieved.

  That is, the present invention resides in an anisotropic membrane compound (Claim 1) characterized in that the form of the free acid is represented by the following formula (1).

(In the above formula (1), X ¹ and X ² each independently represents a —N═N— group or a —NH—CO — (*) group. Note that (*) represents Y ¹ or Y ^2. Represents the binding site.
Y ¹ and ^{Y 2} are each independently a sulfo group, a carboxy _{group, -O (CH 2) n CO} 2 H group or a _{-O (CH 2) m SO 3} H group is at least one substitution, yet another An alkyl group, an alkenyl group, a phenyl group or a naphthyl group which may have a substituent is represented. m and n represent an integer of 1 to 4.
p and q each independently represent 0 or 1, but neither p nor q is 0.
R ^{1 to} R ⁸ each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, an amino group, an acetylamino group, a halogen atom or a hydrogen atom. To express. )

  According to the present invention, it is possible to provide a compound that is useful for an anisotropic film such as a polarizing film and has high dichroism mainly in a short wavelength region and excellent durability.

  Hereinafter, embodiments of the compound for anisotropic film of the present invention will be described in detail.

  The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not specified by these contents.

  The anisotropic film to which the compound for anisotropic film of the present invention is applied is selected from a total of three directions in the thickness direction of a film containing a compound such as a dye and in any orthogonal two-dimensional solid coordinate system. The film has anisotropy in the electromagnetic properties in any two directions. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance. Examples of the film having optical anisotropy such as absorption and refraction include a linearly polarizing film, a circularly polarizing film, a retardation film, and a conductive anisotropic film.

  In the present specification, the term “anisotropic film” refers to a layer containing the compound for anisotropic film of the present invention, and this layer usually contains a low molecular weight material and / or a high molecular weight material. For example, it may be a layer composed only of the compound for anisotropic film of the present invention.

  The anisotropic film compound of the present invention also has a function as a so-called dye, and the anisotropic film containing the anisotropic film compound of the present invention can also function as a dye film. is there. In addition, generally a pigment | dye here means the compound which has absorption in a visible light wavelength range.

The anisotropic film produced using the anisotropic film compound of the present invention is preferably used for a functional film having absorption anisotropy as a main effect, and more preferably used for a polarizing film.

Hereinafter, the anisotropic film compound of the present invention will be described in detail.
In the present invention, “may have a substituent” means that it may have one or more substituents.

  Further, in the present specification, the “total number of carbon atoms of a substituent” represents the number of carbon atoms contained in the substituent, and when the substituent has a further substituent, It is all the carbon numbers including the carbon number contained in a substituent.

1. Compound for anisotropic film 1-1. Compound for Anisotropic Membrane Represented by Formula (1) The anisotropic membrane compound of the present invention is characterized in that the form of the free acid is represented by the following formula (1).

(In the above formula (1), X ¹ and X ² each independently represents a —N═N— group or a —NH—CO — (*) group. Note that (*) represents Y ¹ or Y ^2. Represents the binding site.
Y ¹ and Y ² are each independently a sulfo group, a carboxy group, an —O (CH ₂ ) _n CO ₂ H group or an —O (CH ₂ ) _m SO ₃ H group, An alkyl group, an alkenyl group, a phenyl group or a naphthyl group which may have a substituent is represented. m and n represent an integer of 1 to 4.
p and q each independently represent 0 or 1, but neither p nor q is 0.
R ^{1 to} R ⁸ each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, an amino group, an acetylamino group, a halogen atom or a hydrogen atom. To express. )

The compound for anisotropic film of the present invention is an azo compound having both a stilbene moiety and a bisdisazo structure, and an alkyl group having a water-soluble group in which both ends of the molecule are connected via an azo group or an amide group An azo compound characterized by being an alkenyl group, a phenyl group or a naphthyl group.
The compound for an anisotropic film of the present invention has a stilbene moiety and a stilbene bisdisazo structure in which two disazo moieties are arranged at both ends of the moiety, so that it is rigid while having absorption in a short wavelength region. With a simple molecular shape, a large aspect ratio can be obtained and high dichroism is exhibited. Further, it exhibits high dichroism as a compound having absorption not only in the short wavelength region but also in other regions.
Furthermore, the presence of an alkyl group, alkenyl group, phenyl group or naphthyl group having a water-soluble group via an azo group or an amide group at both ends instead of the inside of the molecule makes the molecule as a whole more rigid and has a large aspect ratio. Although it has water solubility, various substituents can be introduced into the disazo moiety and the terminal alkyl group, alkenyl group, phenyl group or naphthyl group. Since there are also advantages such as easy adjustment, it is highly practical as an anisotropic film compound.

^{<X 1} and ^X 2>
In the formula (1), X ¹ and X ² each independently represent a —N═N— group or a —NH—CO — (*) group. Note that (*) represents a binding site with Y ¹ or Y ² .

^{<Y 1} and ^Y 2>
In Formula (1), each of Y ¹ and Y ² independently has at least one sulfo group, carboxy group, —O (CH ₂ ) _n CO ₂ H group, or —O (CH ₂ ) _m SO ₃ H group. Represents an alkyl group, an alkenyl group, a phenyl group, or a naphthyl group, which may be substituted with another substituent. m and n represent an integer of 1 to 4.
The alkyl group which may have another substituent of Y ¹ and Y ² has a total carbon number of usually 1 or more, usually 6 or less, preferably 4 or less. Examples of the group that may be further substituted on the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, and the like, and specific examples include a methoxy group, a hydroxyl group, a chlorine atom, and the like. .
In the alkenyl group which may have another substituent of Y ¹ and Y ² , the total carbon number of the substituent is usually 1 or more, usually 6 or less, preferably 4 or less. Examples of the group that may be further substituted on the alkenyl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and the like. Specific examples include a methyl group, An ethyl group, a methoxy group, a chlorine atom, etc. are mentioned.
In the phenyl group which may have another substituent of Y ¹ and Y ² , the total carbon number of the substituent is usually 6 or more, usually 12 or less, preferably 9 or less. Furthermore, the naphthyl group which may have another substituent has the total carbon number of a substituent normally 10 or more, usually 15 or less, Preferably it is 12 or less. Examples of the group that may be further substituted on the phenyl group and the naphthyl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group, an acetylamino group, and a hydroxyl group. Specific examples include a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a hydroxyl group, and the like, and preferably has a methyl group, a methoxy group, or a hydroxyl group.
Among the above, Y ¹ and Y ² are other groups in which at least one sulfo group, carboxy group, —O (CH ₂ ) _n CO ₂ H group or —O (CH ₂ ) _m SO ₃ H group is substituted. It is preferably a phenyl group or a naphthyl group which may have a substituent.
Among the above, the substituent for Y ¹ and Y ² is preferably a sulfo group or a carboxy group, and Y ¹ and Y ² are a phenyl group in which one or two sulfo groups or carboxy groups are substituted. Is particularly preferred.

<P and q>
In the formula (1), p and q each independently represent 0 or 1, but neither p nor q is 0.
p and q are preferably both 1 from the viewpoint of solubility in water.

<R ^{1 to} R ⁸ >
In the formula (1), R ^{1 to} R ⁸ are each independently an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, an amino group, or an acetylamino group. Represents a halogen atom or a hydrogen atom.
In the alkyl group which may have a substituent of R ^{1 to} R ⁸ , the total carbon number of the substituent is usually 1 or more, usually 6 or less, preferably 4 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a halogen atom. Specific examples of the alkyl group include a lower alkyl group which may have a substituent such as a methyl group, an ethyl group, an n-propyl group, a hydroxyethyl group, or a 1,2-dihydroxypropyl group.
In the alkoxy group which may have a substituent of R ^{1 to} R ⁸ , the total carbon number of the substituent is usually 1 or more, usually 6 or less, preferably 3 or less. Examples of the group that may be substituted on the alkoxy group include an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a halogen atom. Specific examples of the alkoxy group include a lower alkoxy group which may have a substituent such as a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a hydroxyethoxy group, and a 1,2-dihydroxypropoxy group. Can be mentioned.
Examples of the halogen atom for R ^{1 to} R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
Among these, as R ^{1 to} R ⁸ , a sterically small substituent is preferable from the viewpoint of molecular linearity, and specifically, a methyl group, a methoxy group, an acetylamino group, or a hydrogen atom is preferable. . More specifically, in each combination of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , each other is substituted with a para-position from the viewpoint of molecular linearity. It is preferable.

1-2. Compound for Anisotropic Membrane Represented by Formula (2) The anisotropic compound of the present invention represented by the above formula (1) is a compound for an anisotropic membrane represented by the following formula (2). It is preferable.

（上記式（２）中、Ｙ^１１およびＹ^１２は、それぞれ独立に、スルホ基、カルボキシ基、−Ｏ（ＣＨ_２）_ｎＣＯ_２Ｈ基もしくは−Ｏ（ＣＨ_２）_ｍＳＯ_３Ｈ基が少なくとも一つ置換した、さらに他の置換基を有していてもよいフェニル基またはナフチル基を表す。ｍおよびｎは、１〜４の整数を表す。
Ｘ^１、Ｘ^２、ｐ、ｑおよびＲ^１〜Ｒ^８は、それぞれ独立に、上記式（１）におけると同義である。）
前記式（１）で表される本発明の異方性膜用化合物の中でも、両末端にアゾ基またはアミド基を介してフェニル基またはナフチル基が存在する上記式（２）で表される化合物は、分子全体として剛直で大きいアスペクト比を有し、高い二色性を示すため好ましい。

(In the above formula (2), Y ¹¹ and Y ¹² each independently represent at least a sulfo group, a carboxy group, an —O (CH ₂ ) _n CO ₂ H group or an —O (CH ₂ ) _m SO ₃ H group. It represents a phenyl group or a naphthyl group which may be substituted with one other substituent, and m and n each represent an integer of 1 to 4.
X ^{1, X} 2, p, q and ^R 1 to R ⁸ are each independently has the same meaning as in the formula (1). )
Among the compounds for anisotropic film of the present invention represented by the formula (1), a compound represented by the above formula (2) in which a phenyl group or a naphthyl group is present at both ends via an azo group or an amide group Is preferable because it is rigid as a whole molecule, has a large aspect ratio, and exhibits high dichroism.

^{<Y 11} and ^{Y 12>}
In Formula (2), each of Y ¹¹ and Y ¹² independently has at least one sulfo group, carboxy group, —O (CH ₂ ) _n CO ₂ H group, or —O (CH ₂ ) _m SO ₃ H group. Represents a phenyl group or a naphthyl group which may be substituted with one or more other substituents. m and n represent an integer of 1 to 4.
In the phenyl group which may have another substituent of Y ¹¹ and Y ¹² , the total carbon number of the substituent is usually 6 or more, usually 12 or less, preferably 9 or less. Furthermore, the naphthyl group which may have another substituent has the total carbon number of a substituent normally 10 or more, usually 15 or less, Preferably it is 12 or less. Examples of the group that may be further substituted on the phenyl group and the naphthyl group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group, an acetylamino group, and a hydroxyl group. Specific examples include a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a hydroxyl group, and the like, and preferably has a methyl group, a methoxy group, or a hydroxyl group.
Substituents Y ¹¹ and Y ¹² is preferably a sulfo group or a carboxy group among the above-mentioned, as Y ¹¹ and Y ^12, it sulfo group or a carboxy group is one or two substituted phenyl group Is particularly preferred.

1-3. Compound for Anisotropic Film Represented by Formula (3) The anisotropic compound of the present invention represented by the above formula (2) is a compound for anisotropic film represented by the following formula (3). It is preferable.

(In the formula (3), ^{W 1} and ^{W 2} each independently represent a sulfo group or a carboxy group.
r and s each independently represent 1 or 2.
R ^{1 to} R ⁸ are each independently synonymous with those in the above formula (2). )
Among the compounds for an anisotropic film of the present invention represented by the formula (2), the compound represented by the above formula (3) in which a phenyl group is present at both ends via an amide group is a stilbene bisphenol at the center. Regardless of the structure of the disazo moiety, a phenyl group having a water-soluble group can be easily introduced by amidation. Therefore, the entire molecule is rigid and has a large aspect ratio, while ensuring the water-solubility of the compound, and also has the advantage that the degree of freedom in compound synthesis is large and the desired color tone can be easily adjusted. As a chemical compound, it exhibits high dichroism and is highly practical.

^{<W 1} and ^W 2>
In the formula (3), W ¹ and W ² each independently represent a sulfo group or a carboxy group.
The substitution position is preferably m-position or p-position with respect to the amide group from the viewpoint of molecular linearity. Also, ease of synthesis, W ¹ and W ² are preferably the same.

<R and s>
In the formula (3), r and s each independently represent 1 or 2.

<Molecular weight>
The molecular weight of the compound for anisotropic membrane of the present invention in which the form of the free acid is represented by the formula (1) is preferably 500 or more, more preferably 1500 or less, and more preferably 1300 or less in the form of the free acid. Preferably, 1200 or less is particularly preferable.

<Water-soluble>
The compound for anisotropic film of the present invention is usually a water-soluble compound.

<About salt type>
The compound for anisotropic film of the present invention may be used as it is in the free acid form (free acid form) as shown in the above formulas (1) to (3), and a part of the acid group is salt form. It may be what is. Further, a salt type compound and a free acid type compound may be mixed. Moreover, when it is obtained in a salt form at the time of production, it may be used as it is, or may be converted into a desired salt form (salt exchange). As the salt exchange method, a known method can be arbitrarily used, and examples thereof include the following methods.

1) A strong acid such as hydrochloric acid is added to an aqueous solution of the compound obtained in a salt form, the compound is acidified in the form of a free acid, and then an alkali solution having a desired counter ion (for example, an aqueous sodium hydroxide solution, water) A method in which the acidic group of the compound is neutralized with a lithium oxide aqueous solution or the like to exchange the salt.
2) A method in which a large excess of a neutral salt (for example, sodium chloride, lithium chloride, etc.) having a desired counter ion is added to an aqueous solution of the compound obtained in a salt form, and salt exchange is performed in the form of a salting out cake.
3) An aqueous solution of the compound obtained in a salt form is treated with a strongly acidic cation exchange resin, and the compound is acidified in the form of a free acid, and then an alkali solution having a desired counter ion (for example, sodium hydroxide) Salt exchange by neutralizing the acidic group of the compound with an aqueous solution, a lithium hydroxide aqueous solution or the like).
4) An aqueous solution of the compound obtained in a salt form is allowed to act on a strongly acidic cation exchange resin previously treated with an alkali solution having a desired counter ion (for example, an aqueous solution of sodium hydroxide or an aqueous solution of lithium hydroxide). Method.

  Whether the acidic group of the compound for anisotropic membrane of the present invention is a free acid type or a salt type depends on the pKa of the compound and the pH of the compound solution. Therefore, the acidic group of the compound for anisotropic film of the present invention is free acid type, any salt type, and when there are two or more acidic groups, the free acid type and salt type are mixed or two or more types of salts are used. Can be a variety of molds, such as a mix of molds. In particular, the acidic group of the compound for anisotropic film in the anisotropic film has a preferable pH of the composition for anisotropic film described later and dissociation property to the substrate containing the compound for anisotropic film. Under the influence of the treatment with a solution containing a salt, the salt type may be different from that used in the step of producing the anisotropic film.

Examples of the salt type include salts of alkali metals such as Na, Li, and K, ammonium salts that may be substituted with alkyl groups or hydroxyalkyl groups, and salts of organic amines.
Examples of the alkyl group or hydroxyalkyl group which may be a substituent of the ammonium salt include a lower alkyl group having 1 to 6 carbon atoms and a lower alkyl group having 1 to 6 carbon atoms which are hydroxy-substituted. .
Examples of organic amines include lower alkylamines having 1 to 6 carbon atoms (for example, methylamine, ethylamine, dimethylamine, trimethylamine, etc.), hydroxy-substituted lower alkylamines having 1 to 6 carbon atoms (for example, ethanolamine, Diethanolamine, triethanolamine and the like), carboxy-substituted lower alkylamines having 1 to 6 carbon atoms (for example, carboxymethylamine, carboxyethylamine, carboxypropylamine, dicarboxymethylamine and the like).

In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed. Moreover, multiple types may be mixed in one molecule of a compound, and multiple types may be mixed in the composition.
The preferred type of acidic group of the compound for anisotropic film of the present invention varies depending on the production process of the compound, the content of the composition for anisotropic film described later, preferred pH, etc., but requires high solubility in water. In such cases (for example, when a high compound concentration is required in the composition for anisotropic film in order to enhance the ability of the compound to migrate to the base material), a lithium salt, an ammonium salt, a triethylamine salt, a water-soluble group is present. It is preferable to have one or more substituted organic amine salts or salts thereof. On the other hand, when low solubility in water is required (for example, when it is desired to precipitate the compound from the compound solution in the compound production process), it is in the free acid form, sodium salt, potassium salt, calcium salt, etc. It is preferable to have at least one alkaline earth metal salt or one of these salts.

  Specific examples of the anisotropic film compound in which the form of the free acid is represented by the above formulas (1) to (3) include the following anisotropic film compounds. It is not limited to these.

2. Compound Synthesis Method The compound for anisotropic membrane of the present invention in which the form of the free acid is represented by the above formulas (1) to (3) can be produced according to a method known per se.

  For example, the compound in which the form of the free acid is represented by the formula (1-1) can be produced according to the following steps <1> to <3>.

<1> Using 4,4′-diaminostilbene-2,2′-disulfonic acid in a conventional manner {for example, Yutaka Hosoda, “New Dye Chemistry” (published on December 21, 1978, published by Gihodo), pages 396-409 Page)} and coupled to sodium m-toluidinomethanesulfonate. Subsequently, the stilbene bismonoazo compound is produced by hydrolysis at 90 ° C. in an alkaline aqueous solution.
<2> The obtained stilbene bismonoazo compound is tetrazotized according to a conventional method and coupled to sodium m-toluidinomethanesulfonate. Subsequently, a stilbene bis disazo compound is produced by hydrolysis at 90 ° C. in an alkaline aqueous solution.
<3> The obtained stilbene bis disazo compound is reacted with methyl 4- (chloroformyl) benzoate at 60 ° C. in sodium N-methyl-2-pyrrolidone. Subsequently, hydrolysis is carried out in a mixed solvent of N-methyl-2-pyrrolidone and water at 65 ° C. and pH = 12. After completion of the reaction, salting out with sodium chloride yields a compound having the desired free acid form represented by (1-1) as a sodium salt.

3. Anisotropic film composition In producing an anisotropic film, an anisotropic film composition can be used.
The composition for anisotropic film contains the compound for anisotropic film of the present invention and usually further a solvent, and the compound of the present invention is dissolved or dispersed in the solvent.

In the anisotropic film composition or in the anisotropic film described in detail below, the anisotropic film compound of the present invention can be used alone, but the anisotropy of the present invention can be used alone. Two or more kinds of membrane compounds can be used in combination, or other dichroic substances such as iodine and known dichroic compounds can be used in combination. Furthermore, various solvents, additives, and the like can be used in appropriate combination in order to give desired performance to the produced anisotropic film or to make a composition suitable for production. Furthermore, it can be used by mixing with other compounds such as an ultraviolet absorbing compound and a near infrared absorbing compound to such an extent that the orientation is not lowered. As a result, it is possible to improve the durability of the anisotropic film, correct the hue, improve the polarization performance, and manufacture anisotropic films having various hues.

  As the solvent used in the anisotropic film composition, water, a water-miscible organic solvent, or a mixture thereof is suitable. Specific examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, polyhydric alcohols such as ethylene glycol, 2,2′-thiodiethanol, diethylene glycol, and glycerin, and cellosolves such as methyl cellosolve and ethyl cellosolve. Amide solvents such as 2-pyrrolidone, N-methylpyrrolidone, N, N-dimethylformamide, 1,3-dimethylimidazolidinone, aprotic solvents such as dimethyl sulfoxide and sulfolane, etc. The mixed solvent is mentioned.

  The concentration when the compound for anisotropic film of the present invention is dissolved in these solvents depends on the solubility of the compound and the concentration of the associated state, but is preferably 0.001% by weight or more, more preferably It is 0.01% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.

  In addition, the composition for an anisotropic film may be added with a compound such as urea, thiourea, caprolactam, biuret, semicarbazide, etc., if necessary for improving the solubility of the compound for anisotropic film of the present invention. Additives such as surfactants can be added. As the surfactant, any of anionic, cationic, and nonionic surfactants can be used. These addition concentrations are usually preferably 0.01% by weight or more and 10% by weight or less.

  Furthermore, the anisotropic film composition according to the present invention can use additives as necessary in order to improve the dyeing property to the substrate. Specifically, Asahara Teruzo “New Dye Processing Course Volume 7 Dyeing II”, Kyoritsu Shuppan Co., Ltd., published on June 15, 1972, pages 233-251 and Yamashita Yuya, Nemoto Yoshiro “Polymer Activator” Interfacial Chemistry between Seibundo and Shinko Co., Ltd., published on September 5, 1963, pages 94 to 173, etc. Activators, alcohols, polyhydric alcohols, cellosolves, amide solvents, compounds such as urea and thiourea, and inorganic salts such as sodium chloride and bow nitrate. The addition concentration is usually preferably 0.01% by weight or more and 15% by weight or less.

4). Anisotropic film An anisotropic film can be manufactured using the compound for anisotropic films of this invention.
In addition to the anisotropic film compound of the present invention, the anisotropic film may contain other compounds as necessary, such as known blue dichroic dyes, iodine, and the like surfactants as described above. An additive may be contained. Of course, you may contain combining the compounds represented by the compound for anisotropic films of this invention.
Examples of the method for producing the anisotropic film include the following methods (a) to (d).

(A) A method of dyeing a polymer substrate such as stretched polyvinyl alcohol with a solution (an anisotropic film composition) containing the compound for anisotropic film of the present invention (b) A method of stretching after dyeing a molecular substrate with a solution containing the compound for anisotropic film of the present invention (an anisotropic film composition), etc. (c) Polymer substrate such as polyvinyl alcohol A method of dissolving in a solution such as a solution (an anisotropic film composition) containing the compound for an anisotropic film of the invention and stretching the film after forming a film (d) The compound for an anisotropic film of the present invention Is dissolved in a suitable solvent for film formation (anisotropic film formation)
A composition is prepared, and the film-forming composition is used to form a film on the surface of various substrates such as a glass plate by a wet film-forming method, and the anisotropic film compound contained in the composition is oriented and laminated. How to make

  In the present invention, any of the above (a) to (d) may be used, but it is particularly preferable to use (a) to (c).

  Hereinafter, a method for producing an anisotropic film using the compound for anisotropic film of the present invention will be described. In particular, the above-mentioned (a) to (c) preferably used in the compound for anisotropic film of the present invention. The composition in the case of producing an anisotropic film by the method of) is described in detail.

  In addition, about the method of producing an anisotropic film | membrane by the method of said (d), and the composition used in that case, a well-known method and a composition can be used suitably, For example, international publication 2006 / And the methods and compositions described in US Pat.

  When forming an anisotropic film using the compound for anisotropic film of the present invention, for example, in any of the methods (a) to (c), the compound for anisotropic film of the present invention is appropriately used. Use by dissolving in solvent. As a solvent, the solvent contained in the said composition for anisotropic films is mentioned.

  In addition, the base material dye | stained with the solution containing the compound for anisotropic films of this invention in the method of said (a) and (b), and the compound for anisotropic films of this invention in the method of said (c) Examples of the stretched substrate include polyvinyl alcohol resins, polyvinyl acetate resins, ethylene / vinyl acetate (EVA) resins, nylon resins, and polyester resins. Among them, a polymer material having high affinity with the compound for anisotropic film of the present invention such as polyvinyl alcohol is preferable.

  As the kind of polyvinyl alcohol, those having a high molecular weight and a high saponification degree are generally preferred from the viewpoint of optical properties such as polarization degree and dichroism, but it is possible to suppress defects due to shrinkage due to temperature and humidity and optical properties. For the purpose of achieving both environmental performance and environmental resistance, a polyvinyl alcohol derivative can be selected in which the type of dichroic material and the degree of saponification and modification of the polyvinyl alcohol (ratio of hydrophobic copolymer components) are appropriately adjusted. .

As a specific method for controlling the interaction between the polymer material and the compound for anisotropic membrane of the present invention, proton donating -OH and -NH are added to each of the polymer material and the compound for anisotropic membrane of the present invention. _{2, -NHR, -NHCO -, -} NHCONH- to such proton-accepting _{-N = N -, - OH,} -NH 2, -NRR ', - oR, -CN, -C≡C- and phenyl It can be made effective by combining an aromatic ring such as a group or a naphthyl group as a functional group (R and R ′ are optional substituents). Further, by adjusting the density of the functional group, an effect can be obtained in improving dichroism and dyeing property.

  Dyeing, film formation and stretching in the methods (a) to (c) can be performed by the following general methods.

In the dyeing bath to which the above-mentioned composition for an anisotropic film and, if necessary, an inorganic salt such as sodium chloride and bow glass, and a dyeing assistant such as a surfactant are added, usually at 35 ° C. or higher, usually 80 ° C. or lower. Usually, the polymer film is immersed and dyed for 10 minutes or less, then treated with boric acid as necessary, and dried. Alternatively, the high molecular weight polymer is dissolved in water and / or a hydrophilic organic solvent such as alcohol, glycerin, dimethylformamide, etc., and the composition for anisotropic membrane according to the present invention is added to perform stock solution dyeing. Is formed into a dyed film by casting, solution coating, extrusion, or the like. The concentration of the polymer to be dissolved in the solvent varies depending on the type of polymer, but is usually 5% by weight or more, preferably about 10% by weight or more, and usually 30% by weight or less, preferably 20% by weight. It is about the following. The concentration of the compound for anisotropic membrane of the present invention dissolved in the solvent is usually 0.1% by weight or more, preferably about 0.8% by weight or more, usually 5% by weight, based on the polymer. Hereinafter, it is preferably about 2.5% by weight or less.

  The unstretched film obtained by dyeing and forming a film as described above is stretched in a uniaxial direction by an appropriate method. By performing the stretching treatment, the compound molecule for anisotropic film of the present invention is oriented, and dichroism is expressed. As a uniaxial stretching method, there are a method of stretching by a wet method, a method of stretching by a dry method, a method of compressing and stretching between rolls by a dry method, and the like. May be. The draw ratio is 2 times or more and 9 times or less, but when polyvinyl alcohol and its derivatives are used as the polymer, a range of 3 times or more and 6 times or less is preferable.

  After the stretching and orientation treatment, boric acid treatment is performed for the purpose of improving the durability and the degree of polarization of the stretched film. By the boric acid treatment, the light transmittance and the degree of polarization of the anisotropic film are improved. The conditions for the boric acid treatment vary depending on the type of the hydrophilic polymer used and the anisotropic membrane compound of the present invention, but generally the boric acid concentration is usually 1% by weight or more, preferably 5%. The amount is about 15% by weight or more, usually 15% by weight or less, preferably about 10% by weight or less. Further, the treatment temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher and usually 80 ° C. or lower. When the boric acid concentration is less than 1% by weight or when the treatment temperature is less than 30 ° C., the treatment effect is small, and when the boric acid concentration exceeds 15% by weight or the treatment temperature exceeds 80 ° C. An anisotropic film may become fragile.

The film thickness of the anisotropic film obtained by the methods (a) to (c) is usually 5 μm or more, particularly 10 μm or more, preferably 200 μm or less, and particularly preferably 100 μm or less. If the film thickness is too thick, it may be difficult to reduce the thickness when used in a display. On the other hand, if the film thickness is too thin, the production becomes difficult, which may cause a cost problem.
The concentration of the compound for anisotropic film contained in the anisotropic film obtained by the methods (a) to (c) is usually 0.001% or more, particularly 0.01% or more, preferably 1% or less, In particular, it is preferably 0.5% or less. If the concentration is too low, the polarization performance may be insufficient. On the other hand, if it is too high, the light transmittance is lowered, so that there may be a problem that sufficient luminance as a display cannot be obtained or power consumption is increased.

  The anisotropic film compound of the present invention exhibits a particularly excellent effect in improving dichroism in the short wavelength region, and also exhibits high dichroism not only in the short wavelength region but also in the entire region having absorption. is there. Here, the short wavelength region usually refers to a region near 380 nm to 500 nm, and the anisotropic film compound of the present invention has absorption in this region and expresses high dichroism as one feature. Yes. However, the compound may have absorption also on the longer wavelength side, and the maximum value of absorption may be in the short wavelength region or may not be in the short wavelength region. Any material that absorbs in the above region and exhibits high dichroism can be preferably used.

  The anisotropic film containing the compound for anisotropic film of the present invention utilizes the anisotropy of light absorption and functions as a polarizing film for obtaining linearly polarized light, circularly polarized light, elliptically polarized light, etc. By selecting the composition containing the base material or the compound for anisotropic film of the present invention, it becomes possible to functionalize as various anisotropic films such as refractive index anisotropy and conduction anisotropy, It can be set as a polarizing element applicable to various uses.

  When the anisotropic film is used as a polarizing element, the anisotropic film itself produced by the method represented by the above (a) to (c) may be used, and on the anisotropic film Layers having various functions such as a protective layer, an adhesive layer, an antireflection layer, and a retardation layer may be laminated and used as a laminate.

  When the anisotropic film of the present invention is formed on a substrate and used as a polarizing element, the formed anisotropic film itself may be used. In addition to the protective layer as described above, an adhesive layer or a reflective layer may be used. Various functions such as prevention layer, alignment film, retardation film function, brightness enhancement film function, reflection film function, transflective film function, layer with optical function such as diffusion film A layer having a function may be laminated by a wet film formation method or the like to be used as a laminate.

  These layers having an optical function can be formed, for example, by the following method.

  The layer having a function as a retardation film is subjected to, for example, a stretching process described in JP-A-2-59703, JP-A-4-230704, or a process described in JP-A-7-230007. Or can be formed.

  The layer having a function as a brightness enhancement film may be formed by forming a fine hole by a method as described in, for example, Japanese Patent Application Laid-Open Nos. 2002-169025 and 2003-29030, or the center of selective reflection. It can be formed by overlapping two or more cholesteric liquid crystal layers having different wavelengths.

  The layer having a function as a reflective film or a transflective film can be formed using a metal thin film obtained by vapor deposition or sputtering.

  The layer having a function as a diffusion film can be formed by coating the protective layer with a resin solution containing fine particles.

  The layer having a function as a retardation film or an optical compensation film can be formed by applying and aligning a liquid crystal compound such as a discotic liquid crystal compound or a nematic liquid crystal compound.

  The anisotropic film using the compound for anisotropic film of the present invention can express a wide range of colors and can obtain a highly heat-resistant polarizing element, so that not only a liquid crystal display or an organic EL display is used. It can be suitably used for applications requiring high heat resistance, such as liquid crystal projectors and in-vehicle display panels.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

In the following examples, the dichroic ratio was calculated by the following equation after measuring the transmittance of the anisotropic film with a spectrophotometer in which a prism polarizer was disposed in the incident optical system.
Dichroic ratio (D) = Az / Ay
Az = -log (Tz)
Ay = -log (Ty)
Tz: transmittance for polarized light in the direction of the absorption axis of the anisotropic film Ty: transmittance for polarized light in the direction of the polarization axis of the anisotropic film

[Example 1]
18.5 parts by weight of 4,4′-diaminostilbene-2,2′-disulfonic acid is added to 400 parts by weight of water, and 8 parts by weight of sodium nitrite is added to diazotize under acidic conditions of hydrochloric acid, and m-toluidino. Coupling with 22.3 parts by weight of sodium methanesulfonate under acidic conditions. After the reaction, 17 parts by weight of sodium hydroxide was added and reacted at 90 ° C. for 1 hour to obtain a compound represented by the following formula (1-1a) as a sodium salt.

  25.5 parts by weight of the sodium salt of the compound represented by the formula (1-1a) was dispersed in a mixed solution of 360 parts by weight of N-methylpyrrolidone and 180 parts by weight of water. The mixture was diazotized by adding 6 parts by weight of sodium nitrite under acidic conditions of hydrochloric acid, and coupled with 18.9 parts of sodium m-toluidinomethanesulfonate under acidic conditions. After the reaction, 20 parts by weight of sodium hydroxide was added and reacted at 90 ° C. for 1 hour to obtain a compound represented by the following formula (1-1b) as a sodium salt.

  6.2 parts by weight of the sodium salt of the compound represented by the above formula (1-1b) is dispersed in 100 parts by weight of N-methylpyrrolidone, 2.2 parts by weight of sodium carbonate, methyl 4- (chloroformyl) benzoate 4.2 parts by weight was added and reacted at 60 ° C. for 1 hour. Water was added to the reaction solution, salted out with sodium chloride, and the precipitate was collected by suction filtration. The obtained precipitate is dispersed in 250 parts by weight of water and 100 parts by weight of N-methylpyrrolidone, and subjected to a hydrolysis reaction at 60 ° C. and pH = 12, thereby being represented by the following target formula (1-1). Was obtained as the sodium salt. The maximum absorption wavelength (λmax) of this compound in a 10 ppm aqueous solution was 433 nm.

[Example 2]
4.0 parts by weight of the sodium salt of the compound represented by the formula (1-1b) obtained by the above method is dispersed in 70 parts by weight of N-methylpyrrolidone, 1.4 parts by weight of sodium carbonate, 3- (chlorosulfonyl) ) 3.2 parts by weight of benzoyl chloride was added and reacted at 25 ° C for 3 hours. Water was added to the reaction solution, and a hydrolysis reaction was carried out at 25 ° C. and pH = 9 to obtain the target compound represented by the following formula (1-2) as a sodium salt. The maximum absorption wavelength (λmax) of this compound in a 10 ppm aqueous solution was 442 nm.

[Example 3]
Disperse 5.2 parts by weight of the sodium salt of the compound represented by the formula (1-1b) obtained by the above method in 100 parts by weight of N, N-dimethylformamide, and add 2.5 parts by weight of succinic anhydride. , And reacted at 100 ° C. for 7 hours. Water was added to the reaction solution, pH was adjusted to 7, and salting out with sodium chloride was performed to obtain the target compound represented by the following formula (1-7) as a sodium salt. The maximum absorption wavelength (λmax) of this compound in a 10 ppm aqueous solution was 432 nm.

[Example 4]
Disperse 5.1 parts by weight of the sodium salt of the compound represented by the formula (1-1b) obtained by the above method in 100 parts by weight of N, N-dimethylformamide, and add 2.5 parts by weight of maleic anhydride. , Reacted at 90 ° C. for 5 hours. The target compound represented by the following formula (1-8) was obtained as a sodium salt by crystallization by adding 2-propanol to the reaction solution. The maximum absorption wavelength (λmax) of this compound in a 10 ppm aqueous solution was 437 nm.

[Example 5]
To 100 parts by weight of distilled water, 0.05 part by weight of a sodium salt of the compound represented by the formula (1-1) and 0.02 part by weight of anhydrous sodium sulfate were added and dissolved by stirring to obtain a dyeing solution. A polyvinyl alcohol film (OPL film) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was immersed in this dyeing solution at 50 ° C., dyed, immersed in a 4% by weight boric acid aqueous solution, and stretched to obtain an anisotropic film.
The maximum absorption wavelength (λmax) of this anisotropic film was 463 nm, and it was found that the anisotropic film had a high dichroic ratio.

[Example 6]
The same method as in Example 5 was used except that the sodium salt of the compound represented by the formula (1-2) was used instead of the sodium salt of the compound represented by the formula (1-1). Thus, an anisotropic film was obtained.
The maximum absorption wavelength (λmax) of this anisotropic film was 472 nm, and it was found that the anisotropic film had a high dichroic ratio.

[Example 7]
The same method as in Example 5 was used except that the sodium salt of the compound represented by the formula (1-7) was used instead of the sodium salt of the compound represented by the formula (1-1). Thus, an anisotropic film was obtained.
This anisotropic film has a maximum absorption wavelength (λmax) of 470 nm, and was found to have a high dichroic ratio.

[Example 8]
The same method as in Example 5 was used except that the sodium salt of the compound represented by the formula (1-8) was used instead of the sodium salt of the compound represented by the formula (1-1). Thus, an anisotropic film was obtained.
This anisotropic film has a maximum absorption wavelength (λmax) of 470 nm, and was found to have a high dichroic ratio.

Claims (3)

A compound for anisotropic membrane, wherein the form of the free acid is represented by the following formula (1).

(In the above formula (1), X ¹ and X ² each independently represents a —N═N— group or a —NH—CO — (*) group. Note that (*) represents Y ¹ or Y ^2. Represents the binding site.
Y ¹ and Y ² are each independently a sulfo group, a carboxy group, an —O (CH ₂ ) _n CO ₂ H group or an —O (CH ₂ ) _m SO ₃ H group, An alkyl group, an alkenyl group, a phenyl group or a naphthyl group which may have a substituent is represented. m and n represent an integer of 1 to 4.
p and q each independently represent 0 or 1, but neither p nor q is 0.
R ^{1 to} R ⁸ each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, an amino group, an acetylamino group, a halogen atom or a hydrogen atom. To express. ) The compound for anisotropic film according to claim 1, which is represented by the following formula (2).

(In the above formula (2), Y ¹¹ and Y ¹² each independently represent at least a sulfo group, a carboxy group, an —O (CH ₂ ) _n CO ₂ H group or an —O (CH ₂ ) _m SO ₃ H group. It represents a phenyl group or a naphthyl group which may be substituted with one other substituent, and m and n each represent an integer of 1 to 4.
X ^{1, X} 2, p, q and ^R 1 to R ⁸ are each independently has the same meaning as in the formula (1). ) The compound for anisotropic films according to claim 2, wherein the compound is represented by the following formula (3).

(In the above formula (3), W ¹ and W ² each independently represents a sulfo group or a carboxy group.
r and s each independently represent 1 or 2.
R ^{1 to} R ⁸ are each independently synonymous with those in the above formula (2). )