JP2011122091A - Compound for anisotropic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound for an anisotropic film useful to the anisotropic film such as a polarizing film, and mainly high in dichroism in a short wavelength region and excellent in durability. <P>SOLUTION: The compound for the anisotropic film where the form of a free acid is represented by formula (I) (wherein Ar<SP>1</SP>and Ar<SP>2</SP>are a phenylene group, a naphthylene group or a heterocyclic group, j and k are an integer of 0 to 2, L<SP>1</SP>and L<SP>2</SP>are a -(CH=CH)r- group or a -(C≡C)s- group, r and s are an integer of 1 to 5, X<SP>1</SP>and X<SP>2</SP>are a hydrogen atom or an organic group, Y is an azo group or an azoxy group, and m, n, p and q are 0 or 1) is provided. <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 RGB3 primary colors,
(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, there is a problem that defects due to film shrinkage due to temperature and humidity changes called frame failure or frame unevenness, so that durability at high temperature 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).

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

Although the compound having both the stilbene moiety and the alkenylamide or alkynylamide moiety was considered to be excellent in molecular linearity and dichroic ratio, it has not been improved to obtain a practically sufficient dichroic ratio. There was room.
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.
Another object of the present invention is to provide a compound for an anisotropic film that is excellent in durability and provides a practically sufficient dichroic ratio.

  As a result of intensive studies by the present inventors, it has been found that a compound for an anisotropic film in which the form of the free acid is represented by the following formula (I) 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 (I).

(In the above formula (I), Ar ¹ and Ar ² each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group or an optionally substituted heterocyclic group,
j and k each independently represent an integer of 0 to 2.
L ¹ and L ² each independently represent a — (CH═CH) r— group or — (C≡C) s— group, and r and s each independently represent an integer of 1 to 5;
X ¹ and X ² each independently represent a hydrogen atom or an organic group.
Y represents an azo group or an azoxy group.
m, n, p and q each independently represents 0 or 1, but m, n, p and q are not all 0 at the same time. )

  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 be substituted” means that one or more substituents may be present.

  Further, in this specification, the term “carbon number” of a substituent represents the number of carbon atoms contained in the substituent, and when the substituent has a further substituent, In the case of “carbon number”, it means all the carbon numbers including the carbon number contained in the further substituent.

1. Anisotropic Film Compound The anisotropic film compound of the present invention is characterized in that the form of the free acid is represented by the following formula (I).

(In the above formula (I), Ar ¹ and Ar ² each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group or an optionally substituted heterocyclic group,
j and k each independently represent an integer of 0 to 2.
L ¹ and L ² each independently represent a — (CH═CH) r— group or — (C≡C) s— group, and r and s each independently represent an integer of 1 to 5;
X ¹ and X ² each independently represent a hydrogen atom or an organic group.
Y represents an azo group or an azoxy group.
m, n, p and q each independently represents 0 or 1, but m, n, p and q are not all 0 at the same time. )

  The compound for an anisotropic film of the present invention has a structure site in which the azo group or the azoxy group on both sides of the azo group or the azoxy group is extended with a stilbene moiety at the center of the molecule, and further, an alkenylamide or alkynylamide moiety is present at both ends of the molecule. It is an azo compound having a molecularly extended structural site. Since the stilbene moiety and the alkenylamide or alkynylamide moiety are rigid and have a high molecular linearity, the contribution to the elongation of the pi-electron conjugated system of the azo compound is small. A large aspect ratio can be obtained while having absorption in a short wavelength region, and high dichroism is exhibited. The anisotropic film compound of the present invention exhibits high dichroism as a compound having absorption not only in the short wavelength region but also in other regions.

<Ar ¹ and Ar ² >
In the formula (I), Ar ¹ and Ar ² each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted heterocyclic group. Ar ¹ and Ar ² may be the same or different.

  The optionally substituted phenylene group has a total carbon number of usually 6 or more, usually 15 or less, preferably 12 or less. Examples of the group that may be substituted on the phenylene group include an alkyl group, an alkoxy group, a nitro group, a carboxy group, and an amino group, a methylamino group, a (n) -butylamino group, an acetylamino group, a benzoylamino group, Examples include cinnamoylamino group. Specific examples of the phenylene group which may be substituted include 1,4-phenylene group, 3-methyl-1,4-phenylene group, 2,5-dimethoxy-1,4-phenylene group and the like. A good phenylene group is mentioned.

  The optionally substituted naphthylene group has a total carbon number of usually 10 or more, usually 15 or less, preferably 12 or less. Examples of the group that may be substituted on the naphthylene group include an alkyl group, an alkoxy group, a sulfo group, and a carboxy group. Specific examples of the optionally substituted naphthylene group include 1,4-naphthylene group, 7-sulfo-1,4-naphthylene group, 8-sulfo-1,4-naphthylene group and the like. Groups.

The optionally substituted heterocyclic group is a monovalent heterocyclic group, usually an aromatic heterocyclic group, and an aromatic heterocyclic group having a total carbon number of usually 3 or more, usually 10 or less, preferably 6 or less. It is a group. Examples of the group that may be substituted on the heterocyclic group include an alkyl group, an alkoxy group, a nitro group, a phenyl group, and a carboxy group. Specific examples of the heterocyclic group which may be substituted include a group derived from a pyridine ring, a quinoline ring and a furan ring, and a group derived from a pyridine ring and a quinoline ring is preferable.

Among the above, Ar ¹ and Ar ² are preferably an optionally substituted phenylene group or naphthylene group, and more preferably an optionally substituted phenylene group. In particular, from the viewpoint of reproduction of a specific color tone, the phenylene group is preferably a phenylene group substituted with a lower alkyl group such as a methyl group or an ethyl group, or a lower alkoxy group such as a methoxy group or an ethoxy group. .

<J and k>
In the formula (I), j and k each independently represent an integer of 0 to 2. The preferred values of j and k differ depending on the target color tone, but j and k are preferably 1 as a compound having absorption mainly in the short wavelength region. When j and k are the same integer, the compound molecule has a symmetrical structure centered on the azo group or azoxy group at the center of the molecule.

^{<L 1} and ^L 2>
In the formula (I), L ¹ and L ² each independently represent a — (CH═CH) r— group or a — (C≡C) s— group, and r and s each independently represent 1 to 5 Represents an integer.
As r, from the viewpoint of solubility in water, it is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2. Similarly, s is preferably 1 to 4, more preferably 1 to 3, particularly preferably 1 to 2, from the viewpoint of solubility in water.

^{<X 1} and ^X 2>
In the formula (I), X ¹ and X ² each independently represent a hydrogen atom or an organic group.
The organic group in the present invention refers to a group containing a carbon atom, and specifically includes an optionally substituted alkyl group, a carboxy group, an optionally substituted alkoxycarbonyl group, and an optionally substituted phenyl. Group, an optionally substituted naphthyl group, an optionally substituted heterocyclic group and the like.

  The alkyl group which may be substituted has a total carbon number of usually 1 or more, usually 8 or less, preferably 5 or less. Examples of the group that may be substituted on the alkyl group include an alkoxy group and a carboxy group. Specific examples of the alkyl group which may be substituted include a methyl group and an ethyl group, and a lower alkyl group which may be particularly substituted is preferable.

  The alkoxycarbonyl group which may be substituted has a total carbon number of usually 2 or more, usually 10 or less, preferably 8 or less. Examples of the group that may be substituted on the alkoxycarbonyl group include an alkoxy group, a phenyl group, and a carboxy group. Specific examples of the optionally substituted alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The optionally substituted phenyl group has a total carbon number of usually 6 or more, usually 15 or less, preferably 12 or less. Examples of the group which may be substituted on the phenyl group include an alkyl group, an alkoxy group, a nitro group, a carboxy group, and an amino group, a methylamino group, a (n) -butylamino group, an acetylamino group, a benzoylamino group, Examples include cinnamoylamino group. Specific examples of the optionally substituted phenyl group include optionally substituted phenyl groups such as a phenyl group and a 4-nitrophenyl group.

The naphthyl group which may be substituted has a total carbon number of usually 10 or more, usually 15 or less, preferably 12 or less. Examples of the group that may be substituted on the naphthyl group include an alkyl group, an alkoxy group, and a carboxy group. Specific examples of the optionally substituted naphthyl group include optionally substituted naphthyl groups such as 2-naphthyl group and 6-methyl-2-naphthyl group.

  The optionally substituted heterocyclic group is a monovalent heterocyclic group, usually an aromatic heterocyclic group, and an aromatic heterocyclic group having a total carbon number of usually 3 or more, usually 10 or less, preferably 6 or less. It is a group. Examples of the group that may be substituted on the heterocyclic group include an alkyl group, an alkoxy group, a nitro group, a phenyl group, and a carboxy group. Specific examples of the heterocyclic group which may be substituted include a group derived from a pyridine ring, a quinoline ring, and a furan ring, and a group derived from a furan ring is preferable.

{Preferred X ¹ and X ² }
X ¹ and X ² are each preferably an optionally substituted phenyl group, an optionally substituted alkyl group, a carboxy group or a hydrogen atom. From the viewpoint of dichroism and compound stability, A substituted phenyl group or a phenyl group having one of a nitro group, amino group, carboxy group, hydroxyl group, cinnamoylamino group and benzoylamino group as a substituent is preferable. From the viewpoint of water solubility, a carboxy group is preferred.

<Preferable combination of L ¹ and L ² and X ¹ and X ² >
Among L ¹ and L ² and X ¹ and X ² described above, L ¹ and L ² are —CH═CH— groups, and X ¹ and X ² are optionally substituted phenyl groups. From the viewpoint of dichroism and compound stability, X ¹ and X ² are more preferably a phenyl group. From the viewpoint of water solubility, it is preferable that L ¹ and L ² are —CH═CH— groups, and X ¹ and X ² are carboxy groups.

<Y>
In the formula (I), Y represents an azo group or an azoxy group.
These are obtained in the form of either an azo group or an azoxy group, or a mixture of both, depending on the conditions of the reduction reaction, but may be in any of these forms. Y is preferably an azoxy group or a mixture of an azo group and an azoxy group. Whether Y is an azo group or an azoxy group can be confirmed by acquiring and analyzing mass spectrum data.

<M, n, p and q>
In the formula (I), m, n, p and q each independently represent 0 or 1, but m, n, p and q are not all 0 at the same time. Although preferable values of m, n, p, and q vary depending on the target color tone, m, n, p, and q are preferably 1 as a compound mainly having absorption in a short wavelength region.

<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 (I) is preferably 500 or more, more preferably 2000 or less, and more preferably 1800 or less in the form of the free acid. Preferably, 1500 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 anisotropic film compound of the present invention may be used as it is in the free acid form (free acid form) as shown by the above formula (I), and a part of the acid group is in salt form. It may be a thing. 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 that has been previously treated with an alkali solution having a desired counter ion (for example, an aqueous sodium hydroxide solution, an aqueous lithium hydroxide solution). how to.

  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 compound for anisotropic film in which the form of the free acid is represented by the above formula (I) include the following compounds for anisotropic film, but the present invention is not limited thereto. It is not something.

3. Compound Synthesis Method The compound for anisotropic membrane of the present invention in which the form of the free acid is represented by the formula (11) 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 (11) can be produced according to the following steps <1> to <3>.

<1> Sodium 4-amino-4′-nitrostilbene-2,2′-disulfonate is used in a conventional manner {for example, Yutaka Hosoda, “New Dye Chemistry” (December 21, 1973, published by Gihodo), page 396- Page 409} and is coupled to 2,5-dimethoxyaniline. After completion of the reaction, the monoazo compound is taken out by salting out.
<2> The obtained monoazo compound is dissolved in N-methyl-2-pyrrolidone at room temperature, cinnamic acid chloride and sodium carbonate are added, and acylated at 80 ° C. for 1 hour. After completion of the reaction, the product is discharged into water, and the acylated product is taken out by salting out.
<3> The obtained acylated product is dissolved in water, 30% aqueous sodium hydroxide solution is added to make it strongly basic, then the temperature is raised to 40 ° C., and glucose is added to perform a condensation reaction. After completion of the reaction, the compound is neutralized with hydrochloric acid and then salted out to obtain a compound having a free acid form represented by the formula (11) as a sodium salt.

4). 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 may be used in combination, or other dichroic substances such as iodine and known dichroic compounds may 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 Publishing Co., Ltd., issued on June 15, 1972, pages 233 to 251), Yuya Yamashita and Yoshio Nemoto “ Dyeing aids used for dyeing fibers described in “Surface chemistry of molecular activators and dyeing assistants” (Seikodo Shinko Co., Ltd., issued September 5, 1963, pages 94 to 173), and the like The methods and the surfactants described above, alcohols, polyhydric alcohols, cellosolves, amide solvents, urea, thiourea, and other compounds, and inorganic salts such as sodium chloride and bow glass. The addition concentration is usually preferably 0.01% by weight or more and 15% by weight or less.

5). 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 an appropriate solvent to prepare a film-forming (anisotropic film-forming) composition, and this film-forming composition is used to wet various substrate surfaces such as glass plates by a wet film-forming method. Method of forming a film and orienting and laminating an anisotropic film compound contained in the composition

  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 method of stretching uniaxially, 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, etc., and any method is used. 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 with 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 having absorption in the above region and exhibiting 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]
In 100 parts by weight of distilled water, the following formula No. 0.05 parts by weight of a lithium salt of the compound having the structure of (22) and 0.02 parts by weight of anhydrous sodium sulfate were added and dissolved by stirring to obtain a dyeing liquid (an anisotropic film composition). A polyvinyl alcohol film (OPL film, Nippon Synthetic Chemical Industry Co., Ltd., film thickness 75 μm) is immersed in this dyeing solution at 50 ° C. for 3 minutes for dyeing, and the excess dye is washed in a 50 ° C. water bath. The film was stretched 6 times in 4% by weight boric acid aqueous solution. After stretching, the excess boric acid was washed in a water bath at room temperature and blown and dried to obtain an anisotropic film.
The maximum absorption wavelength of this anisotropic film was 545 nm, the single transmittance at that wavelength was 46.3%, the dichroic ratio was 80, and it had sufficient dyeability and high dichroism.

[Example 2]
No. Instead of the compound of (22), the following formula No. An anisotropic film was obtained in the same manner as in Example 1 except that the lithium salt of the compound having the structure (10) was used.
This anisotropic film had a maximum absorption wavelength of 470 nm, a single transmittance at that wavelength of 53.7%, a dichroic ratio of 60, and had sufficient dyeability and high dichroism.

[Example 3]
No. Instead of the compound of (22), the following formula No. An anisotropic film was obtained in the same manner as in Example 1 except that the sodium salt of the compound having the structure (16) was used.
This anisotropic film had a maximum absorption wavelength of 480 nm, a single transmittance at that wavelength of 46.8%, a dichroic ratio of 64, and had sufficient dyeability and high dichroism.

[Example 4]
No. Instead of the compound of (22), the following formula No. An anisotropic film was obtained in the same manner as in Example 1 except that the sodium salt of the compound having the structure (25) was used and the time for immersion in the staining solution was 5 minutes.
This anisotropic film had a maximum absorption wavelength of 495 nm, a single transmittance at that wavelength of 46.0%, and a dichroic ratio of 66, which had sufficient dyeability and high dichroism.

[Comparative Example 1]
Compound No. 1 of Example 1 In place of (22), the compound (i) described in US Patent Publication No. 2007/0190269, that is, a structure having an azoxy group and two stilbene sites in the center of the molecule but not extended at the alkenylamide site. An anisotropic film was obtained in the same manner as in Example 1 using the lithium salt of the compound having the above.
The maximum absorption wavelength of this anisotropic film is 545 nm, the single transmittance at that wavelength is 47.8%, and the dichroic ratio is 49. It did not show color. It was confirmed that by extending the molecule at the alkenylamide site, high dichroism was exhibited without greatly changing the wavelength.

Claims (1)

A compound wherein the free acid is represented by the following formula (I):

(In the above formula (I), Ar ¹ and Ar ² each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group or an optionally substituted heterocyclic group,
j and k each independently represent an integer of 0 to 2.
L ¹ and L ² each independently represent a — (CH═CH) r— group or — (C≡C) s— group, and r and s each independently represent an integer of 1 to 5;
X ¹ and X ² each independently represent a hydrogen atom or an organic group.
Y represents an azo group or an azoxy group.
m, n, p and q each independently represents 0 or 1, but m, n, p and q are not all 0 at the same time. )