JP2011257489A - Insolubilized anisotropic membrane, insolubilization process liquid, method for producing insolubilized anisotropic membrane, and optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insolubilized anisotropic membrane that does not dissolve in water and that has adequate durability and quality retention property by treating an anisotropic membrane obtained by coating with a solution containing an anisotropic compound such as an organic dye, with insolubilization process liquid; the insolubilization process liquid; a method for producing an insolubilized anisotropic membrane; and an optical element.SOLUTION: The insolubilized anisotropic membrane is an anisotropic membrane that is insolubilized in water and contains an organic dye that shows a lyotropic liquid crystallinity, a cation compound, and an aliphatic monocarboxylic acid.

Description

  The present invention relates to an insolubilized anisotropic film, an insolubilizing treatment liquid, a method for producing an insolubilized anisotropic film, and an optical element.

  In a liquid crystal display (LCD), a polarizing plate, a retardation plate, or the like is usually used to control optical rotation, birefringence, and the like during display. In an organic light-emitting diode (OLED), a circularly polarizing plate is usually used to prevent reflection of external light.

  Conventionally, as these polarizing plates, iodine and an organic dye having dichroism (dichroic dye) are dissolved or adsorbed in a polymer material such as polyvinyl alcohol, and a film made of the polymer material is formed into a film in one direction. A polarizing plate obtained by orienting and orienting a dichroic dye has been widely used. In addition, as a retardation plate, a retardation plate obtained by uniaxially or biaxially stretching various polymer films such as polyvinyl alcohol and polycarbonate has been widely used.

However, in conventional optical elements manufactured with an anisotropic film such as a polarizing plate and a phase difference plate, heat resistance, light resistance, etc. are not sufficient depending on the types of organic dyes and polymer materials used. It was. Another problem is that the yield of film bonding during the manufacture of a liquid crystal device is poor.
Therefore, when a solution containing an anisotropic compound such as an organic dye is applied on a substrate such as glass or a transparent film, the organic dye molecules are oriented on the substrate by a mechanical force such as a shearing force. A method for producing an isotropic membrane has been studied (see, for example, Patent Document 1).

In order to improve the orientation of the anisotropic film obtained by such a method or to obtain a uniform anisotropic film having no defects, a different type containing a water-soluble compound such as amino acids, saccharides, glycerin, and urea is used. An isotropic membrane composition has been studied (see, for example, Patent Document 2).
In addition, in order to improve the durability of an anisotropic film obtained by the same method, an anisotropic film composition containing a drying oil or the like has also been studied (see, for example, Patent Documents 3 and 4). .

However, since anisotropic compounds such as organic dyes usually used for anisotropic films are usually soluble in water that is suitably used as a solvent, the anisotropic films produced by the above coating are There were problems with water resistance and moisture resistance.
In addition, the anisotropic film obtained by the conventional method is made of a solvent in which an anisotropic compound such as an organic dye is dissolved, or a water-soluble compound added for the purpose of improving orientation and suppressing defects. Since a large amount remained in the film, the alignment state of anisotropic compound molecules such as organic dyes was not sufficiently stable on the substrate. Therefore, the durability, quality retention, etc. of the anisotropic films such as polarizing plates and retardation plates usually used for optical elements such as liquid crystal elements are practically insufficient.

  Then, the processing method which insolubilizes the anisotropic film | membrane obtained by such a method in water is also proposed (for example, refer patent documents 5-7 etc.).

Japanese Patent Laid-Open No. 2004-246092 International Publication No. 2005/069048 Pamphlet US Pat. No. 2,544,659 US Pat. No. 2,481,830 Japanese Patent Laid-Open No. 11-21538 JP 2001-337225 A JP 2009-199075 A

However, when insolubilized by the conventional method, the solvent in the anisotropic film and the added water-soluble compound elute out of the film, causing problems such as rapid volume shrinkage, cracking, and loss of orientation. was there.
For example, in Patent Document 7, in order to relieve the volume shrinkage at the time of insolubilization, an insolubilizing solution containing a cationic compound having a relatively large value obtained by dividing the molar volume by a valence and having a valence of 2 or more is used. Although proposed, it has been found that the use of such an insolubilizing solution is insufficient for the above-mentioned problems. Further, in order to improve moisture resistance, increasing the molar volume of the cationic compound contained in the insolubilized liquid, for example, increasing the carbon number of the aliphatic polyamine, the water solubility decreases and the insolubilized liquid becomes non-uniform. As a result, the anisotropic film cannot be insolubilized. That is, there is a limit to reforming a hydrophilic anisotropic film to be oleophilic by a conventional method, and therefore, there is still a problem in durability such as moisture resistance.

  The present invention has been made in view of the above problems, and is dissolved in water by treating an anisotropic film obtained by applying a solution containing an anisotropic compound such as an organic dye with an insolubilizing treatment liquid. The object is to provide an insolubilized anisotropic film having sufficient durability and quality retention. Moreover, it aims at providing the manufacturing method and optical element of this insolubilization process liquid, an insolubilization anisotropic film | membrane.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have obtained a specific compound in the anisotropic film obtained by applying a solution containing an anisotropic compound such as an organic dye. It has been found that the above-mentioned problems can be solved by adding to the present invention, and the present invention has been completed.
That is, the gist of the present invention is an anisotropic film insolubilized in water, characterized by containing an organic dye exhibiting lyotropic liquid crystallinity, a cationic compound, and an aliphatic monocarboxylic acid, It resides in a membrane (claim 1).

Another gist of the present invention resides in an insolubilizing treatment solution characterized by containing a cationic compound and an aliphatic monocarboxylic acid (Claim 5).
Another gist of the present invention is an insolubilization characterized by comprising a step of treating an anisotropic film formed by applying an anisotropic film-forming composition on a substrate with the insolubilization treatment liquid. It exists in the manufacturing method of an anisotropic film | membrane, and the insolubilization anisotropic film | membrane manufactured by this method (Claim 7, 8).

  Furthermore, another gist of the present invention resides in an optical element having the insolubilized anisotropic film (claim 9).

  According to the present invention, in an anisotropic film obtained by applying a solution containing an anisotropic compound such as an organic dye, an insolubilized anisotropic material that does not dissolve in water and has sufficient durability, quality retention, etc. The manufacturing method and optical element of an insoluble film, an insolubilizing treatment liquid, an insolubilizing anisotropic film can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the scope of the invention.

[I. Insolubilized anisotropic film of the present invention]
The insolubilized anisotropic film of the present invention is an anisotropic film insolubilized in water, and contains an organic dye exhibiting lyotropic liquid crystallinity, a cationic compound, and an aliphatic monocarboxylic acid. Isotropic membrane.
Here, the anisotropic film insolubilized in water does not cause appearance changes such as white turbidity, elution, and cracks when immersed in distilled water, and the reduction ratio of the contrast ratio before and after immersion is less than 30%. An anisotropic film is meant. The contrast ratio will be described later.

  Further, in this specification, the “anisotropic film” is different from the electromagnetic property in any two directions selected from a total of three directions in the three-dimensional coordinate system of the film thickness direction and any two orthogonal in-plane directions. It is a film having anisotropy. Examples of the 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. Among them, the insolubilized anisotropic film of the present invention is preferably a polarizing film, a retardation film, or a conductive anisotropic film, and more preferably a polarizing film.

[I-1. Cationic compound]
The insolubilized anisotropic film of the present invention contains a cationic compound as an insolubilizing compound. The cationic compound is preferably contained in the insolubilization treatment liquid of the present invention described later, and is contained in the insolubilized isomer film after treatment by performing insolubilization treatment of the anisotropic film using the treatment liquid. It will be.

In the present specification, the “cationic compound” means a compound that exhibits cation (cationic) property as a dissociated ion state in an aqueous solution in which the compound molecule is dissolved.
The cationic compound used as the insolubilizing compound in the present invention is preferably a compound having a valence of 2 or more.
Here, “valence” represents the sum of the valences of cations generated by 1 mol of the cation compound when the cation compound becomes an ion. For example, bis (hexamethylene) triamine is trivalent because the amine moiety is dissociated when it becomes an ion. Accordingly, in the present invention, bis (hexamethylene) triamine is a trivalent cation compound, and similarly, 1,4-cyclohexanediamine is divalent and pentaethylenehexamine is hexavalent. Further, according to the definition of the present invention, for example, barium chloride and barium chloride dihydrate are divalent, and in the same way, calcium chloride is divalent and lithium chloride is monovalent.

When the valence of the cationic compound is 2 or more, the effect of insolubilizing the anisotropic film in water is higher than when the valence is monovalent.
The molecular weight of the cationic compound is usually 50 or more, preferably 100 or more, usually 500 or less, preferably 300 or less. If the molecular weight is too small, the effects of the present invention may not be obtained. If the molecular weight is too large, the solubility of the cation compound in the solvent will decrease, so the treatment solution will not be uniform or will dissolve evenly when used as a component of the insolubilization treatment solution of the present invention described later. Therefore, the pH of the solvent may have to be lowered. As a result, there is a possibility that the acidic group in the organic dye contained as an anisotropic compound in the insolubilized anisotropic film (insolubilized anisotropic film) becomes a free acid type.

The cationic compound used in the present invention preferably has a value obtained by dividing the molar volume by the valence (hereinafter sometimes referred to as “molar volume / valence value” as appropriate) within a specific range. Here, the molar volume is calculated by dividing the molecular weight of the cationic compound by the specific gravity at 25 ° C. and 101 kPa.
Specifically, in the cation compound, the molar volume / valence, preferably 30 cm ³ / mol or more, more preferably 40 cm ³ / mol or more, more preferably 60cm ³ / mol or more, preferably 200 cm ³ / mol or less, more preferably 120 cm ³ / mol or less.

When the value of molar volume / valence is too small, the effect of the present invention may not be sufficiently obtained. However, a compound having a smaller molar volume / valence value may be used depending on the combination with an aliphatic monocarboxylic acid described later.
In addition, when the molecular weight is too large, the solubility of the cationic compound in the solvent is reduced, so that the treatment liquid may not be uniform when used as a component of the insolubilization treatment liquid of the present invention described later, It may be necessary to lower the pH of the solvent in order to dissolve it. As a result, there is a possibility that the acidic group in the organic dye contained as an anisotropic compound in the insolubilized anisotropic film (insolubilized anisotropic film) becomes a free acid type.

The reason why there is a preferable molar volume / valence value in the cationic compound is that the ratio between the molar volume / valence value of the cationic compound and the molar volume / valence value of the anisotropic compound is different. This is because it is related to the volume change before and after the insolubilization treatment of the isotropic film.
Specifically, in the insolubilization treatment of the anisotropic film, a monovalent cation usually contained in the anisotropic film (usually a counter ion of an organic dye exhibiting lyotropic liquid crystal properties described later) and the above cation compound The anisotropic membrane is insolubilized in water by exchanging its cations. Conventionally, as a cation of the cation compound, a cation having a small volume such as barium has been used. However, when such a cation having a small volume is used, a sufficient effect may not be obtained. It was. The reason is guessed as follows.

That is, when the monovalent cation usually contained in the anisotropic film and the cation of the cation compound are exchanged to insolubilize the anisotropic film, a solvent such as water that usually remains in the anisotropic film in a large amount Since it is released from the film, a compound having a small volume, such as barium, cannot compensate for the volume of the residual solvent to be released, which may cause volume shrinkage of the anisotropic film. This volume shrinkage may cause problems such as macroscopic cracks in the film, and microscopic problems such as disordered arrangement of water-soluble anionic organic compound molecules such as organic dyes. However, the volume is defined by a value per equivalent (that is, a molar volume / valence value), and the volume of water from which the cation of the cationic compound is released by using a cationic compound that is, for example, 30 cm ³ / mol or more. Therefore, a sufficient effect can be obtained.

Here, the reason why the cation compound is defined by the value of molar volume / valence is that the monovalent cation usually exchanged by the insolubilization treatment and the equivalent of the cation compound which is a divalent or higher cation are approximately equal.
Furthermore, it is preferable that the said cation compound is a cation compound which does not have an acidic group from a viewpoint that the insolubilization anisotropic film | membrane of this invention is insoluble with respect to water. Here, the “acidic group” represents a functional group having Arrhenius acid. Specific examples of the acidic group include a carboxy group, a sulfo group, and a phosphoric acid group. That is, the cationic compound is preferably a compound having no acidic group.

The boiling point of the cationic compound is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 50 ° C. or higher, preferably 100 ° C. or higher, more preferably 200 ° C. or higher. If the boiling point is too low, the heat resistance may be lowered.
Examples of the cationic compound contained in the insolubilized anisotropic film of the present invention include polyamine compounds and complex ion compounds, and among them, polyamine compounds are preferable.

A polyamine compound refers to a compound having two or more amino groups in the molecule. In addition, the number of amino groups contained in one molecule of the polyamine compound is usually 2 or more, and the upper limit is usually 20 or less, preferably 10 or less. If the number of amino groups is too small, there is a possibility that the anisotropic film cannot be insolubilized, and if it is too large, the molecular weight increases, so the above compound does not diffuse into the anisotropic film, and may not be insolubilized. There is.

Examples of polyamine compounds include aliphatic polyamine compounds and aromatic polyamine compounds. Of these, aliphatic polyamine compounds are preferred.
Specific examples of the aliphatic polyamine compound include diaminoalkane compounds such as diaminohexane and diaminodecane, diaminocyclohexane such as 1,4-cyclohexanediamine, diaminocycloalkane compounds such as 4,4′-methylenebiscyclohexylamine, and diethylenetriamine. And polyethylene polyamine compounds such as pentaethylenehexamine and bis (hexamethylene) triamine. Among these, a polyethylene polyamine compound is preferable, and bis (hexamethylene) triamine is particularly preferable.

Specific examples of the aromatic polyamine compound include diaminobenzene and xylylenediamine. Of these, diaminobenzene is preferred.
A complex ion compound is a salt of a complex ion formed by coordination bonding of an unshared electron pair in a molecule to a metal ion. Examples of the complex ions of the complex ion compound used in the present invention include tetraammine copper (II) ions and hexaammine cobalt (III) ions.

One kind of the cationic compound may be contained alone in the insolubilized anisotropic film of the present invention, or two or more kinds may be contained in any ratio and combination.
In order to suppress cracking during washing with distilled water in the insolubilization treatment, N- (3-aminopropyl) diethanolamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, It is preferable to use a polyamine having a hydroxyl group such as N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether in combination with the cationic compound.

  The content of the cationic compound contained in the insolubilized anisotropic film of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 5% by weight or more, preferably 10% by weight or more, and usually 40% by weight or less. It is preferably 30% by weight or less. If the amount of the cation compound contained is too small, insolubilization of the anisotropic film may be insufficient, and if it is too large, the anisotropic film may be cracked or the heat resistance may be reduced. There is.

[I-2. Aliphatic monocarboxylic acid]
The insolubilized anisotropic film of the present invention contains an aliphatic monocarboxylic acid in addition to the cationic compound. The aliphatic monocarboxylic acid is preferably contained together with the cation compound in the insolubilization treatment liquid of the present invention described later, and the insolubilization treatment after the treatment is performed by performing the insolubilization treatment of the anisotropic film using the treatment liquid. It is contained in the anisotropic film.

The aliphatic monocarboxylic acid is considered to have a function of helping the cationic compound to be stably taken into the anisotropic film by being used together with the cationic compound used as an insolubilizing compound.
As described above, the insolubilized anisotropic membrane of the present invention is obtained by replacing the cation of the cation compound contained in the insolubilized treatment liquid described later with a monovalent cation that is usually contained in the anisotropic membrane. Insolubilized and manufactured. At this time, the cationic compound alone could not completely compensate for cracks due to rapid volume shrinkage generated in the anisotropic film, a decrease in orientation, etc., but the volume was reduced by using an aliphatic monocarboxylic acid in combination. It was found that the shrinkage can be further suppressed and the conventional problems can be solved.

Further, increasing the molar volume of the cationic compound (for example, increasing the number of carbon atoms of the aliphatic polyamine) in order to improve moisture resistance and the like, the water solubility is lowered and the insolubilized liquid becomes non-uniform and anisotropic. Although the problem that the film could not be insolubilized sometimes occurred, this problem can also be effectively solved because the aliphatic monocarboxylic acid is amphiphilic.
The aliphatic monocarboxylic acid is a compound obtained by substituting a hydrogen atom of an aliphatic hydrocarbon with one carboxyl group, as described in “Large organic chemistry 4. Aliphatic compound III”, Asakura Shoten. Depending on whether the carbon chain is saturated or unsaturated, it is classified as a saturated monocarboxylic acid or an unsaturated monocarboxylic acid, but any monocarboxylic acid can be used.

  In any case of monocarboxylic acids, those having 6 to 30 carbon atoms are preferably used. If the number of carbon atoms is smaller than this, cracks may easily occur during insolubilization, and durability of the insolubilized anisotropic film may be insufficient. On the other hand, if the carbon number is too large, the water solubility of the monocarboxylic acid itself is lowered. Therefore, when this is used as a component of the insolubilization treatment liquid of the present invention described later, the treatment liquid becomes non-uniform and sufficient insolubilization occurs. It may not be possible.

In addition, saturated carboxylic acids increase the number of carbon atoms and have a high melting point, so that the water solubility is significantly reduced.
Specific examples of the aliphatic monocarboxylic acid contained in the insolubilized anisotropic film of the present invention include, for example, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and tridecanoic acid. , Tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, 9-hexadecenoic acid (palmitoleic acid), 9-octadecenoic acid (oleic acid), 11-octadecenoic acid (vaccenic acid), 9,12-octadecadiene Acid (linoleic acid), 9,12,15-octadecantrienoic acid ((9,12,15) -linolenic acid), 6,9,12-octadecatrienoic acid ((6,9,12) -linolenic acid) 9,11,13-octadecatrienoic acid (eleostearic acid), 8,11-icosadienoic acid, 5,8,11
Preferred examples include -icosatrienoic acid, 5,8,11-icosatetraenoic acid (arachidonic acid), and the like.

  The content of the aliphatic monocarboxylic acid contained in the insolubilized anisotropic film of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 1% by weight or more, preferably 5% by weight or more, usually 30%. % By weight or less, preferably 20% by weight or less. If the amount of aliphatic monocarboxylic acid contained is too small, the anisotropic film may crack or heat resistance may be reduced. If it is too much, the surface of the anisotropic film may be roughened. There is sex.

[I-3. Organic dye exhibiting lyotropic liquid crystal properties]
The insolubilized anisotropic film of the present invention contains an organic dye exhibiting lyotropic liquid crystallinity as an anisotropic compound. The organic dye is preferably contained in a composition for forming an anisotropic film, which will be described later, and is contained in the anisotropic film by applying the composition to a substrate. Furthermore, when the formed anisotropic film is insolubilized, the organic dye is contained in the insolubilized anisotropic film of the present invention.

  The organic dye exhibiting lyotropic liquid crystallinity contained in the insolubilized anisotropic film of the present invention is usually an organic dye that is water-soluble and anionic. That is, an anion as a dissociated ion state in an aqueous solution having a functional group such as a carboxy group, a phosphoric acid group, and a sulfo group as a functional group exhibiting water solubility in the molecule and in which the dye molecule is dissolved. (Anion) property.

As described above, in the insolubilization treatment of the anisotropic film, the monovalent cation usually contained in the anisotropic film is exchanged with the cation of the cation compound, so that the anisotropic film becomes free from water. Insolubilized. Usually, the “monovalent cation usually contained in the anisotropic film” is a counter ion of the organic dye exhibiting the lyotropic liquid crystallinity.
As the organic dye, a dichroic dye is usually used. Here, the “pigment” generally means a compound having absorption in the visible light wavelength region.

In this specification, “showing liquid crystallinity” means a state described in “Basics and Applications of Liquid Crystal”, Shoichi Matsumoto and Ryo Tsunoda, 1991, pages 1-16. . In particular, the nematic phase described on page 3 is preferred as the state of the dye solution.
The organic dye exhibiting lyotropic liquid crystallinity contained in the insolubilized anisotropic film of the present invention is contained in the composition for forming an anisotropic film described later, and is applied to a method of forming an anisotropic film by applying it to a substrate. It is preferable that it is suitable.

Specific examples of organic dyes exhibiting lyotropic liquid crystal properties suitable for such methods include azo dyes, stilbene dyes, cyanine dyes, phthalocyanine dyes, condensed polycyclic dyes (perylene-based and oxazine-based). Can be mentioned. Among these organic dyes, azo dyes having high molecular orientation in the insolubilized anisotropic film are preferable.
An azo dye represents an organic dye having one or more azo groups. The number of azo groups in one molecule of the azo dye is preferably 2 or more, preferably 6 or less, more preferably 4 or less from the viewpoint of color tone and production.

  More specifically, for example, azo dyes described in JP2009-199075A, dyes represented by the following formulas (1) and (2), and the like can be given.

(In the above formula (1), A ¹ represents a phenyl group having at least one nonionic electron-withdrawing group as a substituent.
B ¹ , D ¹ and E ¹ each independently represent a divalent aromatic hydrocarbon group which may have a substituent or a divalent heterocyclic group which may have a substituent.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group that may have a substituent, a phenyl group that may have a substituent, or an acyl group that may have a substituent. To express.
m and n represent 0 or 1. )

(In the above formula (2), R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted phenyl group. Represents a group,
A represents the following formula (1-a) or (1-b),

(In the above formula (1-a) or (1-b), R ³ represents a hydrogen atom, a hydroxyl group, or an optionally substituted alkoxy group having 1 to 4 carbon atoms.)
C represents a 1,4-phenylene group which may have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an acetylamino group as a substituent;
n represents 0 or 1. )
In the present specification, “may have a substituent” means that it may have one or more substituents. When it has two or more substituents, the number of substituents may be one, or two or more may be substituted in any ratio and combination.

A preferable type of substituent is appropriately determined from the viewpoint of solubility of organic dye, color tone control, and the like.
The molecular weight of the organic dye exhibiting lyotropic liquid crystallinity contained in the insolubilized anisotropic film of the present invention is preferably 450 or more, preferably 1500 or less, and more preferably 1100 or less in a free acid state. If the molecular weight is too small, the molecular orientation may be inferior. If it is too large, the solubility may be inferior.

  The organic dye as described above has excellent optical properties such as low wavelength dispersibility, high associative property in a solvent such as water and high lyotropic liquid crystallinity, and a high contrast ratio. Therefore, by containing the organic dye, an insolubilized anisotropic film exhibiting high molecular orientation can be obtained.

More preferable specific examples of the organic dye include organic dyes having the structure shown below, but organic dyes exhibiting lyotropic liquid crystallinity contained in the insolubilized anisotropic film of the present invention are limited to the following examples. It is not something.
In addition, the following structural formula represents the form of a free acid. The “free acid form” means that all acidic groups in the molecule are in the free acid form.

Any one organic dye may be included alone in the insolubilized anisotropic film of the present invention, or two or more organic dyes may be included in any ratio and combination.
Furthermore, the insolubilized anisotropic film of the present invention can further contain other organic dyes to such an extent that the molecular orientation is not deteriorated, whereby an anisotropic film such as a retardation film or a polarizing film having various hues. Is obtained.

Furthermore, in addition to the organic dye, for example, a lyotropic liquid crystalline compound or the like may be contained as a water-soluble and anionic organic compound. Thereby, insolubilized anisotropic films such as retardation films and polarizing films having various absorption characteristics can be obtained.
Examples of such other organic dyes and lyotropic liquid crystalline compounds that can be used in combination with the above organic dyes exhibiting lyotropic liquid crystallinity include those described in JP-A-2009-199075. It is done.

  The content of the organic dye exhibiting lyotropic liquid crystallinity in the insolubilized anisotropic film of the present invention is usually 20% by weight or more, preferably 50% by weight or more, and its upper limit is usually 90% by weight or less, preferably Is desirably 80% by weight or less. When the amount of the organic dye is too small, the molecular orientation may be inferior. When the amount is too large, insolubilization of the anisotropic film may be insufficient or the durability may be inferior. In addition, when it contains the organic pigment | dye which shows 2 or more types of lyotropic liquid crystallinity, it is preferable that the sum total of the content satisfy | fills the said range.

  In the insolubilized anisotropic film of the present invention, the value obtained by dividing the content of the organic dye exhibiting lyotropic liquid crystal properties by the content of the cationic compound is usually 2 or more, preferably 3 or more, and the upper limit is It is usually 10 or less, preferably 6 or less. If this value is too small, the molecular orientation may be inferior, and if it is too large, insolubilization of the anisotropic film may be insufficient or the durability may be inferior.

[I-4. Other ingredients]
The insolubilized anisotropic film of the present invention may contain other components in addition to the cationic compound, the aliphatic monocarboxylic acid, and the organic dye exhibiting lyotropic liquid crystallinity. Examples of other components include additives such as surfactants, and molecular orientation improvers such as polyols, amino acids, and taurines. The other components may be used alone or in combination of two or more in any ratio and combination.

  As the surfactant, any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used. Examples of the nonionic surfactant include a polyethylene glycol type and a polyhydric alcohol type. The content of the surfactant is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and the upper limit is 10% by weight or less, preferably 5% by weight. % Or less, more preferably 1% by weight or less. If the amount of the surfactant is too small, there is a possibility that an anisotropic film cannot be formed, and if it is too large, phase separation may occur. Surfactant may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios and combinations.

Furthermore, as additives other than those described above, for example, “Additives for Coating”, Edited by J. et al. Known additives described in Bieleman, Willy-VCH (2000) and the like can also be used.
In the insolubilized anisotropic film of the present invention, as other components, a cation compound having a valence of not less than 30 cm ³ / mol and having a molar volume / valence of less than 30 cm ³ / mol (hereinafter referred to as “other cation compound”). In some cases, the molar volume / valence value obtained by calculating the volume average of the cation compound and the other cation compound is preferably 30 cm ³ / mol or more. Furthermore, it is preferable that the total amount of the cation compound and other cation compounds satisfy the content range of the cation compound. As for other cationic compounds, one type may be included alone, or two or more types may be included in any ratio and combination.

Said volume average can be calculated | required according to the method described below, for example.
That is, first, based on the structure and weight fraction of each compound obtained by composition analysis of the insolubilized anisotropic film of the present invention, the volume fraction is determined using the specific gravity of each compound. And the value of the molar volume / valence of each compound is calculated | required using the valence calculated | required from the measured structure of each compound. By calculating the product of the obtained volume fraction and the value of molar volume / valence, the volume average of each compound can be determined.

[I-5. Physical properties]
The film thickness of the insolubilized anisotropic film of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but the film thickness after drying is preferably 10 nm or more, more preferably 50 nm or more, The upper limit is preferably 30 μm or less, more preferably 10 μm or less. If the insolubilized anisotropic film is too thin, it may be difficult to obtain a uniform film thickness. If it is too thick, the molecular orientation of the organic dye molecules constituting the insolubilized anisotropic film is controlled. Can be difficult.

  The contrast ratio of the insolubilized anisotropic film of the present invention is usually 10 or more, preferably 50 or more, more preferably 100 or more. When the contrast ratio is too small, it is not suitable as an insolubilized anisotropic film. The contrast ratio is measured, for example, by measuring the transmittance of the insolubilized anisotropic film with a spectrophotometer (SolidSpec 3700 manufactured by Shimadzu Corp.) in which a Grand Taylor type polarizing element is arranged in the incident optical system, and then JIS (Japan Standards Association). In accordance with the color measurement method of a transparent object specified in Z8701 (1995) and Z8722 (1994), color calculation is performed in a double field of view under a D65 standard light source, and can be calculated by the following equation.

Y _y : Lightness (Y value) calculated based on the transmittance for polarized light in the polarization axis direction of the insolubilized anisotropic film
Y _z : Lightness (Y value) calculated based on the transmittance for polarized light in the absorption axis direction of the insolubilized anisotropic film
The insolubilized anisotropic film of the present invention is an anisotropic film insolubilized in water. An anisotropic film insolubilized in water is excellent in that when the anisotropic film is immersed in distilled water, it does not cause changes in appearance such as white turbidity, elution, and cracks, and does not cause deterioration in various optical properties after immersion. Have the advantages. Here, in order to represent the degree of insolubilization, the contrast ratio can be used as an index.
Specifically, in the insolubilized anisotropic film of the present invention, the reduction rate of the contrast ratio after immersion when compared before and after immersion is usually less than 30%, preferably 20% or less, more preferably 10% or less. It is.

[II. Insolubilized treatment liquid of the present invention]
The insolubilizing treatment liquid of the present invention is characterized by containing a cationic compound and an aliphatic monocarboxylic acid.
[II-1. Cationic compound used in insolubilizing solution]
The insolubilizing treatment liquid of the present invention contains a cationic compound. Preferably, the value obtained by dividing the molar volume by the valence is 30 cm ³ / mol or more, and contains a cationic compound having a valence of 2 or more.

Examples of the cationic compound contained in the insolubilizing treatment solution of the present invention include [I-1. The same thing as what is contained in the insolubilized anisotropic membrane of this invention demonstrated by the cation compound] is used. A cationic compound may be used individually by 1 type, and may be used 2 or more types by arbitrary ratios and combinations.
The amount of the cationic compound contained in the insolubilization treatment liquid of the present invention is appropriately selected based on the solubility of the anisotropic compound contained in the anisotropic film in the insolubilization treatment liquid. The upper limit is usually 10% by weight or more, preferably 15% by weight or more, and the upper limit is usually 40% by weight or less, preferably 30% by weight or less. If the concentration is too low, the anisotropic film may be dissolved during the insolubilization process, and if it is too high, it may be difficult to clean the anisotropic film after the insolubilization process.

[II-2. Aliphatic monocarboxylic acid used in insolubilizing solution]
The insolubilization process liquid of this invention contains aliphatic monocarboxylic acid with the said cation compound. Examples of the aliphatic monocarboxylic acid contained in the insolubilizing treatment solution of the present invention include [I-2. The thing similar to what is contained in the insolubilized anisotropic film of this invention demonstrated by the aliphatic monocarboxylic acid] is used. As the aliphatic monocarboxylic acid, one kind may be used alone, and two kinds or more may be used in optional ratio and combination.

  The amount of the aliphatic monocarboxylic acid contained in the insolubilizing treatment liquid of the present invention is sufficient to neutralize the solubility of the anisotropic compound contained in the anisotropic film in the insolubilizing treatment liquid and the cationic compound. However, the upper limit is usually 50% by weight or less, preferably 30% by weight or less, based on the insolubilization treatment liquid. Is desirable. If the concentration is too low, the durability may be insufficient. If the concentration is too high, the viscosity of the insolubilized liquid may be too high, and cleaning after the insolubilization treatment may be difficult.

  Such aliphatic monocarboxylic acid salts are known to easily form nanometer-order molecular aggregates such as micelles due to their amphipathic properties. From the viewpoint of easiness of insolubilization treatment and durability of the insolubilized anisotropic film, the insolubilizing solution is preferably a transparent solution in which a molecular assembly of nanometer order is formed. If the insolubilized solution is cloudy, the aliphatic monocarboxylic acid is less likely to be taken into the anisotropic film, and the effect may not be sufficiently exhibited.

  In addition, what is necessary is just to adjust the quantity of the cation compound and aliphatic monocarboxylic acid in the final insolubilization process liquid based on the following method. That is, for example, when dissolution of the anisotropic film is observed because the insolubilization treatment liquid is colored after the insolubilization treatment, the amount of the cationic compound contained in the insolubilization treatment liquid may be increased. . On the other hand, when the anisotropic film is observed with a polarizing microscope or the like and processing unevenness or partial cracks are generated, there is a possibility that the cleaning is insufficient, so the cationic compound contained in the insolubilized processing liquid Reduce the amount. The amount of the aliphatic monocarboxylic acid may be an amount that neutralizes the cation compound in the insolubilization treatment solution, and can be adjusted according to the amount of the cation compound.

[II-3. solvent]
The insolubilizing treatment liquid of the present invention usually contains a solvent capable of dissolving the cationic compound and the aliphatic monocarboxylic acid.
Examples of the solvent used for the insolubilizing treatment liquid include water, sulfuric acid, acetic acid, hydrochloric acid and the like. A solvent may be used individually by 1 type and may be used 2 or more types by arbitrary ratios and combinations.
The insolubilizing treatment liquid may contain a water-soluble organic solvent in addition to the above-mentioned solvent for the purpose of improving the solubility of the cationic compound or suppressing the dissolution of the anisotropic film. As the water-soluble organic solvent, in addition to the organic solvent freely mixed with water and a single layer, the water-soluble organic solvent is mixed at a ratio of usually 5% by weight or more and usually less than 100% by weight at the solution temperature during the insolubilization treatment (Dissolvable) and the like can be mentioned.

  Specific examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentyl alcohol, 3-methyl-2-butanol and the like. Lower alcohols having a carbon number of usually 1 or more and 5 or less; dimethyl ketone (acetone), methyl ethyl ketone, diethyl ketone, acetonyl acetone, cyclohexanone, etc. Ketones: dimethyl ether, methyl ethyl ether, diethyl ether, diethylene oxide (1,4-dioxane), tetrahydrofuran or the like, which is usually a chain or cyclic ether having 1 or more and usually 4 or less carbon; ethylene glycol diethyl ether, ethylene Glycols such as glycol dimethyl ether. Among them, alcohols, ketones, and ethers are preferable, and isopropyl alcohol, dimethyl ketone, methyl ethyl ketone, 1,4-dioxane, and tetrahydrofuran are particularly preferable from the viewpoint of high solubility in water. In addition, any one of these water-soluble organic solvents may be used alone, or two or more thereof may be used in combination in any ratio and combination.

  When the insolubilizing treatment liquid contains a water-soluble organic solvent, the amount of the water-soluble organic solvent in the insolubilizing treatment liquid depends on the solvent used in the insolubilizing treatment liquid, the cationic compound and fat of the present invention to the contained water-soluble organic solvent, etc. Although it is appropriately determined depending on the solubility of the group monocarboxylic acid, it is usually 3% by weight or more, preferably 5% by weight or more, and the upper limit thereof is usually 99% by weight or less, preferably 95% by weight with respect to the insolubilized solution. Below, more preferably 50% by weight or less, still more preferably 20% by weight or less, and particularly preferably 10% by weight or less. If the amount of the water-soluble organic solvent is too small, the effect of using the water-soluble organic solvent may be small. On the other hand, when there is too much quantity of a water-soluble organic solvent, the solubility of the cation compound and aliphatic monocarboxylic acid in an insolubilization process liquid falls, and a cation compound and aliphatic monocarboxylic acid may precipitate. In addition, when using 2 or more types of water-soluble organic solvents together, it is preferable to make it the total concentration of those water-soluble organic solvents fall in the said range.

[II-4. Surfactant]
The insolubilizing treatment liquid may contain a surfactant in addition to the cationic compound, the aliphatic monocarboxylic acid and the solvent. As the surfactant, any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used, but a nonionic surfactant is preferable. Examples of the nonionic surfactant include a polyethylene glycol type and a polyhydric alcohol type. Any one of these surfactants may be used alone, or two or more thereof may be used in combination in any ratio and combination.

[II-5. Other ingredients]
The insolubilizing treatment liquid may contain other components other than those described above as long as the effects of the present invention are not significantly impaired. For example, if the anisotropic film before the insolubilization treatment contains a molecular orientation improver such as polyol, amino acid, or taurine, the insolubilization treatment liquid is used for the purpose of suppressing the elution of the molecular orientation improver. The same molecular orientation improver may be contained. The content of other components can be arbitrarily determined as long as the insolubilized anisotropic film of the present invention is obtained.

[II-6. Preparation of insolubilizing solution]
The method for preparing the insolubilized treatment liquid is not particularly limited. For example, the cationic compound and the aliphatic monocarboxylic acid may be mixed with a solvent so as to be in the above concentration range, and stirred as necessary to dissolve in the solvent. Moreover, you may mix said water-soluble organic solvent, surfactant, etc. which are used as needed into a solvent so that it may become said concentration range, respectively. The mixing timing, order, and the like are arbitrary, and the components described above may be mixed in any order at any time as long as the insolubilized anisotropic film of the present invention is obtained.

[III. Method for producing insolubilized anisotropic film of the present invention]
The method for producing an insolubilized anisotropic film of the present invention comprises a step of treating an anisotropic film formed by applying an anisotropic film forming composition on a substrate with the insolubilizing treatment liquid of the present invention (hereinafter referred to as “insoluble film”). And at least “insolubilization treatment step”). The method for producing an insolubilized anisotropic film of the present invention comprises a step of forming an anisotropic film by applying a composition for forming an anisotropic film on a substrate (hereinafter referred to as “an anisotropic film forming process” as appropriate). And at least two steps of the insolubilization treatment step.

An insolubilized anisotropic film is obtained by performing an insolubilization process step on the anisotropic film.
In general, the insolubilization treatment is a treatment in which ions having a lower valence are replaced with ions having a higher valence (that is, for example, a monovalent ion is replaced with a multivalent ion) as in the production of a lake pigment. That is. More specifically, for example, “Toyo Hosoda,“ Theoretical Manufacturing Dye Chemistry ”, Gihodo, (1957), pages 435 to 437, Chapter 10. Organic pigments and pigment printing and undiluted dyeing Section 10.2 Lake (Lake)” Represents the processing described in the above.

  In the following description, the method for producing an insolubilized anisotropic film of the present invention will be described by taking as an example a production method having two steps of an anisotropic film formation step and an insolubilization treatment step. However, the content described below is an example of the method for producing an insolubilized anisotropic film of the present invention, and can be arbitrarily changed without departing from the gist of the present invention.

[III-1. Anisotropic film formation process]
(substrate)
In the present invention, the anisotropic film is usually formed on an arbitrary substrate.

  As the substrate, for example, a substrate such as glass, triacetate, acrylic, polyester, triacetyl cellulose, norbon-based, cyclic polyolefin-based or urethane-based film is directly used, and the surface of these substrates is subjected to, for example, corona treatment, plasma. Examples of the substrate include a substrate subjected to a known surface treatment such as treatment and ultraviolet ozone treatment, and a substrate obtained by subjecting the substrate surface to a known liquid crystal alignment treatment such as polyimide. It may be a single substrate or a film substrate. The thickness of the substrate is usually 0.01 mm or more, preferably 0.02 mm or more, and usually 3 mm or less, preferably 1 mm or less.

  Further, the surface on which the anisotropic film is formed or the back surface thereof is subjected to various functions that constitute an optical element such as a liquid crystal element such as a micro color filter, an active drive element, an ITO electrode, and an antiglare film, before the film is formed. May be. A board | substrate may be used individually by 1 type and may be used by arbitrary ratios and combinations of 2 or more types.

(Orientation treatment)
In order to control the molecular orientation of organic dyes exhibiting lyotropic liquid crystal properties that are usually used as anisotropic compounds on the substrate surface, “Liquid Crystal Handbook”, published by Maruzen Co., Ltd., published on October 30, 2000, An orientation treatment is performed in one direction by a known method described on pages 226 to 239 and the like. In the present invention, this orientation-treated direction is referred to as “orientation treatment direction”. Specific methods include, for example, a method of providing directionality after forming a uniform thin film on the substrate surface, and a method of forming a thin film while providing directionality to the substrate surface.

Among these methods, in the former, for example, first, a polyamic acid monomer that is a polyimide precursor monomer, a photocurable resin monomer, a polymer such as polyester is applied in a solution state, and post-treatment such as drying is performed. To form a uniform thin film. Thereafter, the thin film may be rubbed with a rayon cloth or the like, or directivity may be imparted to the whole or a part of the thin film surface by irradiating electromagnetic rays such as ultraviolet rays or electron beams. Here, in this specification, “rubbing” means “planting cloth or the like on a cylindrical roller as described in“ Liquid crystal display manufacturing device terminology ”edited by Japan Semiconductor Manufacturing Equipment Association, Nikkan Kogyo Shimbun, page 21. This represents rotating the wound material on a thin film, rubbing, stretching the surface layer, and orienting the axis of the resin surface of the orientation material.
Further, in the latter case, for example, a polymer substrate in which oblique deposition of silicon oxide is performed on the substrate surface, a resin piece such as polytetrafluoroethylene is rubbed in one direction on the substrate surface, and the resin thin film is transferred to the substrate surface. Examples of the method include stretching in a uniaxial direction.

  More specifically, for example, a polyamic acid (eg, San-Ever 610 manufactured by Nissan Chemical Co., Ltd.) is used as a base layer on a glass substrate (eg, AN100 manufactured by Asahi Glass, thickness 0.7 mm to 1.1 mm) as silk. A film (for example, a thickness of 500 nm to 2000 nm) formed by printing, spin coating, slot die coating or the like is preheated at 100 ° C. to 150 ° C. and subjected to a dehydration condensation reaction at 200 ° C. to 300 ° C. to obtain a polyimide film. As the underlayer, polyester, polyvinyl alcohol, polyacetate, or the like can be used. A substrate (including a base layer) is fixed, and a roll (for example, a diameter of 30 mm to 30 mm) wound with a rubbing cloth (for example, polyethylene, rayon, cotton, etc.) with a certain amount of pushing (for example, 0.2 mm to 1 mm) on the substrate. 100 mm) is pressed and the roll is rotated (for example, rotation speed 100 rpm to 5000 rpm) while moving the substrate (for example, speed 3 mm / second to 500 mm / second) to obtain an alignment treatment film made of a polyimide film. it can. As another method for producing the alignment film, there is an oblique deposition film of silicon dioxide or a film obtained by vacuum-depositing diamond-like carbon, and the like.

  Among these, particularly preferable is that even if a micro color filter, an active drive element circuit, or the like is formed on the front surface or the back surface of the substrate, the molecular orientation of the organic dye is controlled, and the electric power of an optical element such as a liquid crystal element is used. A polyimide film formed by baking polyamic acid at 250 ° C. or less, which is hardly adversely affected by optical properties and the like, and is rubbed using a roll of a rayon rubbing cloth.

(Anisotropic film forming composition)
In the anisotropic film forming step of the production method of the present invention, an anisotropic film is usually formed by applying a composition for forming an anisotropic film on a substrate that has been aligned in one direction (that is, the alignment processing direction). Form. The composition for forming an anisotropic film used in the present invention may be a material containing at least an organic dye exhibiting lyotropic liquid crystallinity, and may be a solution or a gel material. In the composition for forming an anisotropic film, one kind of organic dye exhibiting lyotropic liquid crystallinity may be contained alone, or two or more kinds thereof may be contained in any ratio and combination.

The anisotropic film-forming composition usually contains an organic dye exhibiting lyotropic liquid crystallinity and a solvent.
Any organic dye exhibiting lyotropic liquid crystallinity can be used as long as the effects of the present invention are not significantly impaired. Among them, [I-3. It is preferable to use the organic dye described in [Organic Dye Showing Lyotropic Liquid Crystallinity].

  In the present invention, the organic dye exhibiting lyotropic liquid crystallinity contained in the composition for forming an anisotropic film may be one in which all acidic groups of the organic dye are in a free acid form. All / or a part of the groups may have a salt form. Further, an organic dye having an acid group that is a salt type and an organic dye having an acid group that is a free acid type may be mixed. Moreover, when an acidic group is obtained in a salt form at the time of manufacturing the organic dye, it may be used as it is, or the acidic group may be converted into a desired salt form. As an exchange method for converting an acidic group into a salt form, 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 an organic dye obtained in a salt form, the organic dye is acidified in the form of a free acid, and then an alkali solution having a desired counter ion (for example, an aqueous lithium hydroxide solution) ) To neutralize the acidic group of the organic dye and perform salt exchange.
2) A method of performing salt exchange in the form of a salting-out cake by adding a large excess of a neutral salt (eg, lithium chloride) having a desired counter ion to an aqueous solution of an organic dye obtained in a salt form.

3) An aqueous solution of an organic dye obtained in a salt form is treated with a strongly acidic cation exchange resin, and the organic dye is acidified in the form of a free acid, and then an alkaline solution having a desired counter ion (for example, water A method of neutralizing an acidic group of an organic dye with a lithium oxide aqueous solution and performing salt exchange.
4) A method of performing salt exchange by allowing an aqueous solution of an organic dye obtained in a salt form to act on a strongly acidic cation exchange resin previously treated with an alkaline solution having a desired counter ion (for example, an aqueous lithium hydroxide solution). .
Whether the acidic group of the organic dye has a free acid form or a salt form usually depends on the pKa of the organic dye and the pH of the aqueous dye solution.

  Examples of the salt type include salts of alkali metals such as sodium, lithium and potassium, and salts of ammonium or organic amine which may be substituted with an alkyl group or a hydroxyalkyl group. Examples of the organic amine include a lower alkylamine having usually 1 or more and usually 6 or less carbon atoms, a lower alkylamine having 1 or more and usually 6 or less carbon atoms substituted with a hydroxyl group, and a carbon number substituted with a carboxy group. A lower alkylamine of usually 1 or more and usually 6 or less is mentioned. In the case of these salt forms, the kind is not limited to one kind, and two or more kinds may be mixed in an arbitrary ratio and combination.

The composition for forming an anisotropic film used in the present invention can contain other organic dyes to such an extent that the molecular orientation is not lowered in addition to the organic dyes described above. An anisotropic film such as a retardation film and a polarizing film can be produced.
Other organic dyes can be included as long as the effects of the present invention are not significantly impaired. Among these, other organic dyes are preferably organic dyes having absorption in the visible light wavelength region. Specific examples of the organic dye having absorption in the visible light wavelength region include [I-3. And the like described in [Organic dye]. In addition, another organic pigment | dye may be used individually by 1 type, and may use 2 or more types by arbitrary ratios and combinations.

In addition, other lyotropic liquid crystalline compounds that can be contained in the composition for forming an anisotropic film include, for example, [I-3. And the like as described in [Organic dye exhibiting lyotropic liquid crystallinity].
Any one of these compounds may be used alone, or two or more thereof may be used in any ratio and combination. Thereby, anisotropic films such as a retardation film and a polarizing film having various absorption characteristics can be manufactured.

(Solvent used for composition for anisotropic film formation)
The solvent used in the composition for forming an anisotropic film is arbitrary as long as the effects of the present invention are not significantly impaired. Among them, water, a water-miscible organic solvent, or a mixture thereof is preferable, but usually Use water. Specific examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin, and cellosolves such as methyl cellosolve and ethyl cellosolve. In addition, a solvent may be used individually by 1 type and may use 2 or more types by arbitrary ratios and combinations.

(Concentration of anisotropic compound in the composition for forming an anisotropic film)
The concentration of the organic dye exhibiting lyotropic liquid crystallinity in the composition for forming an anisotropic film is arbitrary as long as the effects of the present invention are not significantly impaired. However, for example, when water is used as the solvent, the concentration of the organic dye is usually 0.01% by weight or more, preferably 0.1% by weight or more, and the upper limit is usually 50% by weight or less, preferably 30% by weight. % Or less. If the concentration of the organic dye is too low, an anisotropic film having sufficient optical properties such as light transmission and dichroism may not be obtained. There is a possibility that organic pigments precipitate in the composition.

(Other components such as additives used in the composition for forming an anisotropic film)
The composition for forming an anisotropic film may further contain other components such as an additive such as a surfactant and a pH adjuster, if necessary. These other components can improve the wettability, applicability, and the like of the composition for forming an anisotropic film. The other components may be used alone or in combination of two or more in any ratio and combination.

Examples of the surfactant include [I-4. Examples thereof include the same surfactants as described in “Other components”. The amount of the surfactant used is normally 0.05% by weight or more and usually 0.5% by weight or less based on the composition for forming an anisotropic film. Surfactant may be used individually by 1 type, and may use 2 or more types together by arbitrary ratios and combinations.
Further, from the viewpoint of improving the stability of the anisotropic compound in the composition for forming an anisotropic film and suppressing the occurrence of salt formation, aggregation and the like, the pH adjuster is added to the composition for forming an anisotropic film. May be mixed to adjust the pH. The pH adjuster can usually be arbitrarily selected from known acids, alkalis and the like. The timing for adding the pH adjusting agent is not particularly limited, and the pH adjusting agent may be added at any stage before, during or after mixing of the components of the anisotropic film forming composition.

(Application of composition for anisotropic film formation)
As a method for applying the anisotropic film-forming composition to a substrate, for example, “Coating Engineering”, Yuji Harasaki, Asakura Shoten, published March 20, 1971, pages 253 to 277, “Molecules” Known methods described in “Creation and application of cooperative materials”, supervised by Kunihiro Ichimura, CMC Publishing Co., Ltd., published on March 3, 1998, pages 118 to 149, and the like. In addition, for example, a spin coating method, a spray coating method, a bar coating method, a roll coating method, a blade coating method, a curtain coating method, a fountain method, a dip method, etc. are applied to a substrate that has been previously subjected to an alignment treatment. Can be mentioned.

  The temperature at the time of application | coating on the board | substrate of the composition for anisotropic film formation is 0 degreeC or more normally, and the upper limit is 80 degrees C or less normally, Preferably it is 40 degrees C or less. Moreover, the humidity at the time of application | coating is 10 RH% or more normally, Preferably it is 30 RH% or more, and the upper limit is usually 80 RH% or less. Note that RH is an abbreviation for Relative Humidity, and RH% represents relative humidity.

(Thickness of anisotropic film)
The physical properties, components, etc. of the anisotropic film before the insolubilization process produced by the above steps are arbitrary as long as the effects of the present invention are not significantly impaired. However, the thickness of the anisotropic film before the insolubilization treatment is [I-5. The film thickness of the insolubilized anisotropic film of the present invention described in Physical Properties] is usually the same.
(Concentration of anisotropic compound in anisotropic film)
Further, the content of the organic dye exhibiting lyotropic liquid crystallinity contained in the anisotropic film before the insolubilization treatment is arbitrary as long as the effects of the present invention are not significantly impaired. However, the content of the organic dye contained in the anisotropic film before insolubilization treatment is [I-3. It is usually the same as the content in the insolubilized anisotropic film of the present invention described in [Organic dye exhibiting lyotropic liquid crystallinity].

  Further, the contrast ratio of the anisotropic film before the insolubilization treatment is usually 10 or more, preferably 50 or more, more preferably 100 or more. If the contrast ratio is too small, it is not suitable as an anisotropic film. The contrast ratio is, for example, [I-5. It can be calculated using a method similar to the method described in Physical Properties].

[III-2. Insolubilization process]
Next, the insolubilized anisotropic film of the present invention is obtained by subjecting the anisotropic film formed in the anisotropic film forming process to an insolubilizing process. That is, the insolubilized anisotropic film of the present invention can be obtained by treating the anisotropic film obtained in the anisotropic film forming step with the insolubilizing solution of the present invention.

(Insolubilization method)
The method for insolubilizing the anisotropic film is not particularly limited as long as the insolubilizing solution of the present invention can be brought into contact with the anisotropic film. As a specific example of the method of insolubilization treatment, an insolubilization treatment liquid is put in a bath such as a bat, and an anisotropic film formed by applying an anisotropic film forming composition on a substrate is insolubilized together with the substrate. Examples include a method of dipping in a liquid, a contact method in which an insolubilized liquid is brought into contact with an anisotropic film by various coating methods such as spraying and die. The temperature during the insolubilization treatment depends on the components in the anisotropic film, but is usually 20 ° C. or higher and usually 25 ° C. or lower.

  In addition, the said insolubilization process process may be performed only once and may be performed twice or more as long as the insolubilized anisotropic film of this invention is obtained. Moreover, as long as it is after the said anisotropic film formation process, you may perform the order arbitrarily combining with the other process mentioned later. Specifically, for example, after the insolubilization treatment of the anisotropic film is performed once, the insolubilization anisotropic film may be dried as another process, and the insolubilization treatment may be further performed on the obtained anisotropic film. . Further, for example, after the second insolubilization treatment, the insolubilized anisotropic film may be further dried.

[III-3. Other processes]
In the method for producing an insolubilized anisotropic film of the present invention, as long as the insolubilized anisotropic film of the present invention is obtained, it has optional steps other than the anisotropic film forming step and the insolubilizing treatment step. Also good. Other steps may be performed only once, or may be performed twice or more as long as the insolubilized anisotropic film of the present invention is obtained.

Above all, as other processes, the insolubilized anisotropic solution is insolubilized with an air knife or the like, a process of washing (rinsing) the insolubilized anisotropic film with water so that no solids remain on the insolubilized anisotropic film after the insolubilization process. It is preferable to have a step of rinsing after removal from the anisotropic film and a drying step of further drying after rinsing.
In order to further enhance the durability of the insolubilized anisotropic film, a step of drying after being immersed in a solution containing an unsaturated carboxylic acid, such as semi-drying oil or drying oil, or being applied on the film, is performed. It is also preferable to have it.

[IV. Advantages of insolubilized anisotropic film of the present invention]
The insolubilized anisotropic film of the present invention has high molecular orientation, does not dissolve in water (water-insoluble), and is stable at high humidity, preventing re-dissolution of the dye film (deliquefaction) with water vapor, etc. And is less likely to cause defects, exfoliation, and the like (that is, excellent durability, quality retention, etc.), and can be handled stably.

More specifically, since the insolubilized anisotropic film of the present invention is stable against external changes such as temperature, humidity, and atmospheric pressure, for example, a polarizing plate or a plate usually used for an optical element such as a liquid crystal element. As a phase difference plate or the like, excellent optical characteristics can be maintained in a wide range of environments.
In the insolubilized anisotropic film of the present invention, the organic dye exhibiting lyotropic liquid crystallinity contained in the insolubilized anisotropic film is insoluble in water due to the presence of the cationic compound and the aliphatic monocarboxylic acid. Become. Therefore, the insolubilized anisotropic film of the present invention has high stability and durability with respect to various processes such as a cleaning process.

  Further, when the anisotropic film of the present invention is heat-treated, there is no volatilization of the residual solvent, so there is no deterioration of optical characteristics, surface roughness, and the like. Therefore, even if the insolubilized anisotropic film of the present invention is fused with a film or overcoated with a thermosetting resin, the quality such as optical properties as an anisotropic film is little deteriorated. There is also an advantage that it is excellent in retention.

[V. Use of insolubilized anisotropic film of the present invention]
(Optical element)
Various post-processes are added to the insolubilized anisotropic film of the present invention as necessary, and application to an optical element becomes possible. That is, the optical element of the present invention has the insolubilized anisotropic film of the present invention. Further, for example, the insolubilized anisotropic film of the present invention can be used with a protective layer provided if necessary. This protective layer is formed by lamination with a transparent polymer film such as triacetate, acrylic, polyester, polyimide, triacetylcellulose, norbon-based, cyclic polyolefin-based or urethane-based film, and is practically used as an optical element. be able to.

  The insolubilized anisotropic film of the present invention can be directly formed on a high heat resistant substrate such as glass. Therefore, from the viewpoint that an optical element such as a highly heat-resistant polarizing element or retardation element can be obtained, the anisotropic film of the present invention is not limited to a liquid crystal display, an organic EL display, etc. It can be suitably used for applications that require high heat resistance, such as display panels.

Further, since the insolubilized anisotropic film of the present invention is excellent in stability such as water insolubility and is less likely to cause defects and peeling, the In-- of the liquid crystal element manufactured through many water washing steps. Application to a cell type polarizing film, an in-cell type phase difference film and the like can also be expected.
Among them, the insolubilized anisotropic film of the present invention is preferably used for a polarizing film, a retardation film, and a conductive anisotropic film, more preferably used for a retardation film and a polarizing film. It is particularly preferable to use it for applications. In particular, when the contrast ratio of the insolubilized anisotropic film is large, specifically, the insolubilized anisotropic film of the present invention is used when the contrast ratio is usually 100 or more, particularly 500 or more, and even 1000 or more. This is desirable because the effect obtained by is increased.

The insolubilized anisotropic film of the present invention can be used as a polarizing film or the like in various optical elements (display elements) such as liquid crystal displays and organic light emitting diodes. In this case, an insolubilized anisotropic film of the present invention is directly formed on the surface of an electrode substrate or the like constituting these optical elements, and a substrate on which the insolubilized anisotropic film of the present invention is formed is formed. What is necessary is just to use as a structural member of these optical elements.

  The insolubilized anisotropic film of the present invention may be an optical absorption anisotropy (ie, polarization) and / or a refractive index anisotropy (ie, birefringence), either alone or in combination of two or more. And functions as a polarizing film for obtaining linearly polarized light, circularly polarized light, elliptically polarized light, and the like. Furthermore, the insolubilized anisotropic film of the present invention is made anisotropic by selecting an anisotropic film forming step, a substrate, and an anisotropic film forming composition containing an organic dye as necessary. It can be functionalized as various anisotropic films such as conductivity and conduction anisotropy, and can be applied to various types of optical elements that can be used for various purposes.

The optical element of the present invention thus has the insolubilized anisotropic film of the present invention. When the insolubilized anisotropic film of the present invention is formed on a substrate, the optical element of the present invention is formed. In addition, the formed insolubilized anisotropic film itself may be used, and in addition to the protective layer described above, layers having various functions such as an adhesive layer and an antireflection layer are laminated and used as a laminate. Also good.
The layer having these optical functions can be formed, for example, by the following method. First, a layer having a function as a retardation film is subjected to stretching treatment described in, for example, JP-A-2-59703 and JP-A-4-230704, or described in JP-A-7-230007. It can be formed by subjecting to other processing.

In addition, the layer having a function as a brightness enhancement film may be formed by, for example, a method of forming micropores described in JP-A Nos. 2002-169025 and 2003-29030, and / or a central wavelength of selective reflection. Can be formed by superimposing two or more cholesteric liquid crystal layers having different values.
Furthermore, the layer which has a function as a reflective film or a transflective film can be formed using the metal thin film obtained by vapor deposition, sputtering, etc., for example.

The layer having a function as a diffusion film can be formed, for example, 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.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless it deviates from the summary. In the following description, “parts” means “parts by weight” unless otherwise specified.
The contrast ratio (CR) between the anisotropic film and the insolubilized anisotropic film is determined by a spectrophotometer (SolidSpec 3700 manufactured by Shimadzu Corporation) in which a Grand Taylor-type polarizing element is arranged in the incident optical system. After measuring the transmissivity of the membrane, the color calculation in the 2 degree visual field is performed under the D65 standard light source in accordance with the color measuring method of the transparent object specified in JIS (Japanese Standards Association) Z8701 (1995) and Z8722 (1994). And calculated by the following formula.

Y _y : Lightness (Y value) calculated based on the transmittance of the anisotropic film or insolubilized anisotropic film with respect to the polarized light in the polarization axis direction
Y _z : Lightness (Y value) calculated based on the transmittance for polarized light in the absorption axis direction of the anisotropic film or insolubilized anisotropic film

[Example 1]
In 79.48 parts of water, 12.46 parts of 100% lithium neutralized salt of the dye represented by the following formula (A), 0.54 parts of 50% lithium neutralized salt, glycylglycylglycine 1.08 manufactured by Tokyo Chemical Industry Co., Ltd. Part, DL-aspartic acid 3.07 part by Tokyo Chemical Industry Co., Ltd., and L-(+)-lysine 3.37 parts by Tokyo Chemical Industry Co., Ltd. were stirred and dissolved to prepare a dye solution.

A polyimide alignment film (polyimide film thickness of about 80 nm) is formed on a glass substrate (75 mm × 150 mm, thickness 0.7 mm) by a silk printing method, and a rubbing treatment is performed in advance in the long side direction of the substrate with a cloth. The applied one was prepared as a substrate. On this alignment film, the above-mentioned dye solution is applied at a speed of 235 mm / second in parallel with the long side direction of the substrate with an applicator (manufactured by Horita Seisakusho) gap of 4 μm, and dried to form an anisotropic film. did. The application conditions were 23 ° C. and 40RH% to 60RH%.
As a result of measuring the optical characteristics of the obtained anisotropic film with a spectrophotometer, the contrast ratio was 560.

On the other hand, in 70.4 parts of water, bis (hexamethylene) triamine manufactured by Tokyo Chemical Industry Co., Ltd. (compound having a molar volume / valence value of 80 cm ³ / mol and having a trivalent valence (see Table 1 below)) 3.6 parts, N- (3-aminopropyl) diethanolamine manufactured by Tokyo Chemical Industry Co., Ltd. (compound having a molar volume / valence value of 90 cm ³ / mol and a divalent valence (see Table 1 below)) 4 .4 parts, 12.7 parts of decanoic acid manufactured by Tokyo Chemical Industry Co., Ltd., and 8.9 parts of linoleic acid manufactured by Tokyo Chemical Industry Co., Ltd. were added and dissolved by stirring to obtain a slightly yellowish transparent insolubilizing solution. The substrate on which the anisotropic film was formed was dipped in this insolubilizing treatment solution for 2 seconds, washed with distilled water, and blown and dried to perform insolubilizing treatment.

  The insolubilized anisotropic film obtained after the insolubilization treatment was a uniform and good film without cracks, dropping off of the film and the like. As a result of measuring the optical characteristics at the same location as before the insolubilization of the obtained insolubilized anisotropic film with a spectrophotometer, the contrast ratio was 490, and the optical characteristic decrease rate by the insolubilization treatment was as small as 13%. Further, even when the insolubilized anisotropic film was immersed in distilled water, the dye was not dissolved in the distilled water, and a decrease in contrast ratio in the insolubilized anisotropic film before and after the immersion was not observed.

[Comparative Example 1]
Example 1 is the same as Example 1 except that an aqueous solution obtained by adding 75.6 parts of 6N sulfuric acid to 24.4 parts of bis (hexamethylene) triamine manufactured by Tokyo Chemical Industry Co., Ltd. An anisotropic film was formed and insolubilized by the same procedure. The anisotropic film was cracked in the coating film during the insolubilization treatment, and completely peeled off during washing with distilled water.

  Table 1 summarizes the molar volume / valence values and the numerical values necessary to obtain the values of the compounds used as the cationic compounds in the above Examples and Comparative Examples.

Claims (9)

  An anisotropic film insolubilized in water, comprising an organic dye exhibiting lyotropic liquid crystallinity, a cationic compound, and an aliphatic monocarboxylic acid. 2. The insolubilized anisotropic film according to claim 1, wherein the cationic compound is a compound having a value obtained by dividing a molar volume by a valence of 30 cm ³ / mol or more and having a valence of 2 or more. .   The insolubilized anisotropic film according to claim 1 or 2, wherein the cationic compound is a polyamine compound.   The insolubilized anisotropic film according to any one of claims 1 to 3, wherein the cationic compound is a compound having no acidic group.   A solution for insolubilization comprising a cationic compound and an aliphatic monocarboxylic acid. The insolubilizing treatment liquid according to claim 5, wherein the cationic compound is a compound having a value obtained by dividing the molar volume by a valence of 30 cm ³ / mol or more and having a valence of 2 or more.   An insolubilized anisotropy comprising a step of treating an anisotropic film formed by applying an anisotropic film-forming composition on a substrate with the insolubilizing treatment liquid according to claim 5 or 6. A method for producing a membrane.   An insolubilized anisotropic film produced by the production method according to claim 7.   An optical element comprising the insolubilized anisotropic film according to claim 1.