JPS61285259A - Dichroic dye and polarizing film containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (Y is ( or S; X1-X6 are H, halogen or (substituted) amino; Q is group of formula II or III [R1 and R2 are H, halogen, methyl, etc.; m is 1-3; R3 is COOH, -COOR4, CONH2, -CONHR4 or -COCR4 [R4 is (substituted) phenyl, naphthalene group, etc.]; X7-X13 are H, halogen, (substituted) amino, etc.}). EXAMPLE:The compound of formula IV. USE: Polarizing film having excellent moisture-resistance and heat-resistance. PREPARATION:The objective compound can be produced by the ring-closing condensation reaction of the compound of formula V (X1'-X6' are X1-X6) with the carboxylic acid chloride compound of formula VI (R1'-R3' are R1-R3) or formula VII (X7'-X13' are X7-X13) in an inert solvent such as nitrobenzene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a dichroic dye and a polarizing film using the same, and more particularly to a novel polarizing film particularly excellent in moisture resistance and heat resistance.

[Conventional technology]

Polarizing films that are commonly used today use polyvinyl alcohol-based resin as the film base material, and are coated with dichroic substances such as iodine compounds and/or acid dyes or direct dyes with selected structures. It has polarization properties.

The durability of this type of polarizing film is usually maintained by covering both sides of the film with a film-like material (hereinafter referred to as a protective film layer) that is moisture resistant and transparent on at least one side. That is, measures have been taken to obtain practical durability by protecting the drawbacks of the internal polarizing film layer (hereinafter referred to as polarizer layer), which inherently has extremely poor durability, with protective film layers on both sides.

Polarizing films have already been used in large quantities as an important component of liquid crystal display devices, but as the field of use for liquid crystal display devices expands, the durability of the polarizing films used has to be improved, especially moisture resistance. There is a strong demand for improved heat resistance.

Various proposals have been made to solve these demands, but
These can be summarized into three methods. The first method uses a polarizer that is a combination of a conventional polyvinyl anodichol resin and a water-soluble dichroic dye, while the protective layer is made of an acetate cellulose resin, which is more durable than polyvinyl alcohol. This is a method of protecting with acrylic resin, polyester resin, polyurethane resin, etc., and it is possible to considerably improve durability with this method, but the polarizer exposed at the cut portion of the polarizing film has low moisture resistance and polarization. There is a limit to the durability improvement due to the low heat resistance of the child base resin itself.

The second method is to use a hydrophobic polymer film having a conjugated double bond in a polyene structure as a polarizing film, but although the moisture resistance is improved, there is a change in transmittance due to an increase in the polyene structure due to heat, etc. It has drawbacks such as a low degree of polarization, and has not yet been technically perfected. The third method is an attempt to obtain a polarizing film or polarizer by coloring a hydrophobic polymer represented by polyester, polyamide, etc. with a dichroic dye and stretching it. = belongs to this method.According to the third method, in principle, a fundamental solution to issues such as moisture resistance and heat resistance can be achieved.However, in reality, in such hydrophobic polymers, There are few proposals for dichroic dyes that exhibit high dichroism, and the reality is that the completion of polarizing film manufacturing technology using such methods is limited.

As a known technology for durable polarizing film,
JP 57-84409 and JP 57-84409 by the present inventors
-68008 etc. are exemplified. Both are dichroic dyes developed for liquid crystals that have been applied to polarizing films.

[Problem that the invention seeks to solve]

This type of polarizing film can be used immediately after production using conventional PVA.
In some cases, it has a polarizing performance comparable to that of other polarizing films, but when used for a long time, especially when used in a heated state, the polarizing ability decreases significantly, which poses a practical problem. The main reason for this is that dichroic dyes for liquid crystals are generally structurally selected to be dissolved in the liquid crystal material in as high a concentration as possible. However, the molecules of such dyes, for example, This is thought to be due to the fact that in a hydrophobic resin film base material such as polyethylene terephthalate, it moves more easily due to thermal movement (2), especially when heated, and disturbs its own alignment. In the process, measures are taken to prevent film shrinkage, etc. and to obtain dimensional stability, usually by a heat treatment process following the stretching process.

When using dyes that have extremely high solubility in hydrophobic base resins, such as dichroic dyes for liquid crystals, the degree of polarization may be quite high immediately after the stretching process, but during the heat treatment process After this process, the degree of polarization decreases significantly.Therefore, in order to obtain a polarizing film with a high degree of polarization, this type of polarizing film must be heat-set after the stretching process. Therefore, it is not possible to obtain a product with sufficient dimensional stability and a stable degree of polarization because heat treatment cannot be performed for 20 minutes, and vice versa. If so, sufficient heat treatment must be performed after the stretching process, so
A product with a high degree of polarization was not obtained.

An object of the present invention is to provide a novel dichroic dye that is suitable for coloring hydrophobic polymers and has excellent transparency, moisture resistance, and weather resistance.

Another object of the present invention is to provide a novel polarizing film in which a hydrophobic polymer is used as a film base material and the novel dichroic dye is oriented and contained therein.

[Means for solving the problems] As a result of various studies to solve these problems, we have found that the most important requirements for dyes used in polarizing films that use hydrophobic resin as a film base material to solve the above problems are as follows: The inventors have discovered that the most important characteristic is to have high dichroism, and that they must also have certain pigment suitability, and have arrived at the present invention.

The present invention is based on the general formula (1), [in formula (1), Y is an oxygen atom or a sulfur atom, and x
l, x2. x, , x, , x, and X6 are hydrogen atoms, halogen atoms, hydroxy groups, or carbon atoms of 1 to
It is an amino group optionally substituted with three alkyl groups, and Q is a monovalent a group represented by formula (I[), or formula (m). Here, in formula (II), R
8 and R2 are a hydrogen atom, a halogen atom, a methyl group,
or a methoxy group, m is an integer of 112 or 3, and R5 is -COOH, -COOR,.

-CONH2, -CONHR, -〇0CR4, -NH
COR4, -N=N-R4゜phrase R,, R1, -COOH and/or -COOCH3
is an optionally substituted phenyl group, biphenyl group or naphthalene group. In formula (m), X7. X,
.

x, , x, o, x, , , x, and Xl,
is an amino group optionally substituted with a hydrogen atom, a halogen atom, a hydroxy group, or an alkyl group having 1 to 3 carbon atoms. When X7 is an amino group or both X7 and X9 are nia-amino groups, x, , x, , x3.
x,, x,, x,.

x, , x, , x, o, x, , x, □ and Xl are not hydrogen atoms at the same time] This is a new dichroic dye.

Still another aspect of the present invention provides a hydrophobic polymer containing the general formula (
This is a polarizing film containing an oriented dichroic dye represented by I).

These dichroic organic dyes of the present invention are suitable for polarizing films, and have dichroism and at the same time are substantially insoluble in water, organic solvents, and liquid crystals. Here, "substantially insoluble"
This means that at room temperature, that is, about 25° C., the dichroic dye has a 0.0.
0.05% by weight or less, preferably 0.01% by weight or less. In addition, the organic solvents used here include acetone, methyl alcohol, ethyl alcohol, chloroform, benzene, toluene, xylene, nitrobenzene, chlorobenzene, 0-dichlorobenzene, N, N
- A readily available inert organic solvent with a boiling point of 250° C. or lower, such as dimethylformamide or ethyl acetate. Furthermore, liquid crystals include liquid crystals that have a nematic phase or smectic phase that is fluid at room temperature, such as Schiff base liquid crystals, biphenyl liquid crystals, phenylcyclohexyl liquid crystals, ester liquid crystals, pyrimidine liquid crystals, and mixtures thereof. It is.

As described above, an important property of the novel dichroic dye of the present invention is that it is substantially insoluble in organic solvents and liquid crystals, and this property is due to the fact that the dye of the present invention is substantially insoluble in organic solvents and liquid crystals. This indicates that it has a certain pigment suitability. Such dyes are suitable for use in polarizing films based on hydrophobic polymers.
This means that it is impossible to select based on chromaticity by dissolving it in liquid crystal and determining whether or not it has excellent dichroism. That is, the means for determining whether the dichroic dye of the present invention has excellent dichroism suitable for use in polarizing films has not necessarily been clear.

The present inventors measured the dichroism of the dye in polyethylene terephthalate, which is a typical example of a hydrophobic polymer, as a simple and effective means of evaluating the dichroism of the dye. This method was used to determine the suitability of the dye to be applied. The method involves uniformly mixing an appropriate amount of pigment into a pellet of polyethylene terephthalate with an intrinsic viscosity of 0.6 to 0.75, melting it to form a film, and then thinning it in the longitudinal direction at a temperature near or above the glass transition temperature. Tomo 3
As a sample, a film obtained by stretching the free width more than twice
This method measures the dichroic ratio of a dye at the maximum absorption wavelength within the visible light region. The novel dichroic dye of the present invention has a dichroic ratio of 7 or more as measured by such a method, and is made of aromatic polyester polymers such as polyethylene terephthalate and other hydrophobic polymers as a film base material. It is suitable as a dye for polarizing films.

Using the methods and criteria described above, it is now possible to easily select a dye that has pigment suitability, which has traditionally been difficult to determine whether it has sufficiently high dichroism for use in polarizing films. .

The dichroic dye of the present invention is a dichroic dye having a novel structure suitable for a polarizing film based on a hydrophobic polymer, which was discovered based on the above-mentioned method and criteria.

The dye of the present invention will be explained in more detail.

The dye of the present invention is a novel dye represented by general formula (I).

The dye represented by the general formula (I) has the general formula (Ia)
, (In formula (Ia), X; + X'2 * XS + Kari,
X2 and Kari are derivable or substitutable groups, and Y is of the formula (
The compound represented by formula (IIa) is a di-derivatable or substitutable group, and m is the same as in formula (n). ) or general formula (Ha), X et OXl.

(In formula (ma), X'T + XQ + X'o + x
,. A carboxylic acid chloride compound represented by l , condensation, ring closure, induction into a group, or substitution reaction (=Thus, synthesis is possible.

Representative examples of the novel dichroic dyes of the present invention that can be synthesized in this manner are shown in Table 1.

Table 1 0H OH ONH2 ONH2 In the production of the polarizing film of the present invention, the dye used can be used in its crude form, but it is preferably purified using recrystallization or other purification means. Further, it is preferable to use the powder after pulverizing it to a size of several microns or less.

The polarizing film of the present invention contains at least one of the above-mentioned dyes, and in order to obtain a desired hue, and especially to obtain a neutral gray polarizing film, it is preferable to select and mix several kinds of dyes. Furthermore, it may be used in combination with a dichroic dye other than the one of the present invention, or in some cases, a non-dichroic dye or other polarizing substance.

The dye of the present invention as described above has extremely suitable performance as described above for use in a polarizing film based on a hydrophobic polymer. The polarizing film of the present invention can be obtained using these dyes.

The hydrophobic polymer in the present invention is not particularly limited as long as it is an organic polymer compound having a linear structure that does not contain hydrophilic groups in its molecular structure, but it preferably has thermoplasticity. Examples of the resin include vinyl polymer, acrylic, polyolefin, polyamide, polyimide, polyester, polycarbonate, and polyethersulfone resins. Among these, those containing at least 80% by weight of aromatic polyester resin components such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, which have excellent heat resistance, moisture resistance, and transparency, are particularly preferred.

The amount of the dye to be used relative to the base polymer, which is a hydrophobic polymer as described above, is determined by taking into consideration the coloring ability of the dye and the desired thickness of the polarizing film, but preferably one polarizing film to be obtained. Visible light transmittance per unit is 3
Adjust so that it is 0 to 60%. For standard dyes, if the thickness of the polarizing film is 30 to 200 microns, the amount of dye to base resin (2) ranges from 0.01 to 10% by weight.

In order to produce the polarizing film of the present invention, the base polymer and at least one selected from the above dyes are melted and colored together with other dyes mixed if necessary, and then formed into a film or sheet, and then After stretching 3 to 10 times in the vertical or horizontal direction at a temperature of ~150°C,
It can be produced by heat treatment at 0 to 230°C for 1 second to 30 minutes.

Although it is sufficient to stretch the film in only one direction, if necessary, the film may be stretched approximately 1.1 to 2 times in a direction perpendicular to the main stretching direction to improve the mechanical strength of the film.

The polarizing film manufactured in this way can be processed into various types of films and sheets depending on the purpose and put to practical use. That is, a) the film produced by the above method as it is, b) a protective film on one or both sides of which is optically transparent and has excellent mechanical strength, such as colored or uncolored glass or synthetic resin. C) Polarizing sheet or film with a film layer; C) Polarizing sheet or film with adhesive applied on one or both sides for ease of application to commonly used liquid crystal displays, window glasses, glasses, etc. Further examples include d) a polarizing film in which a transparent conductive film such as an indium-tin oxide is added to the surface by a well-known method such as vapor deposition, sputtering or coating. These can also be used as cell forming materials for liquid crystal display elements.

In addition, the dye of the present invention can be applied not only to the polarizing film, but also to other forms by utilizing dichroism, such as melting and kneading the dye of the present invention with a hydrophobic polymer similar to that used in the polarizing film. By processing it into a stretched fiber (2), it can be used for fibers with rich color rendering properties or for clothing-like clothing, etc. It is also useful as a general resin coloring material.That is, it basically has the properties required for resin coloring materials such as heat resistance, light resistance, -sublimation resistance, and bleed resistance. It is also suitable for coloring hydrophobic polymers, such as polystyrene, polypropylene, polyethylene, polyamide, polyimide, polyester, etc., with excellent transparency.In this way,
The dye of the present invention can be used without being limited to polarizing films.

〔Example〕

Hereinafter, representative examples (two examples) of the dye of the present invention and a polarizing film using the dye will be specifically described.

Note that the degree of polarization in Examples is a value measured by the following method. That is, the light transmittance ('r++) at the maximum absorption wavelength in the visible region measured by placing two polarizing films on top of each other so that the stretching directions are parallel to each other and placing them in the optical path of a spectrophotometer, and The degree of polarization (V) was calculated using the following formula from the light transmittance (T) at the same wavelength measured overlappingly so as to be orthogonal.

Example 1 (Table 1, dye synthesis of dye number 1) 15 g of 2-amino-3,4-dihydroquine-1-nitro-anthraquinone, 17 g of piphenyl-4,4'-dicarboxylic acid monochloride and zinc chloride II After stirring at 70°C for 2 hours in 200ml of orthodichlorobenzene, the mixture was further stirred at 170-180°C for 10 hours, and after cooling, 100d of methanol was added, the precipitate was filtered, and the F mass was washed with methanol and water. The obtained F mass was dispersed in 500 d of ethanol, 100 g of an aqueous solution containing 14.51 d of 60% sodium sulfide was added, stirred under reflux for 10 hours, filtered under heat, washed with methanol and water, and dried. did. Crude dye 18.1.9 was obtained. After pulverization, soluble impurities were removed by Soxhlet extraction using acetone, and dried to obtain a reddish-purple powdered pigment (Table 1,
Dye No. 1, m, p, >300°C) was obtained.

Dye 0.5.9 to nitrobenzene 100! After heating in i, it was left to stand at 25°C for several hours. The supernatant liquid was slightly colored red, but most of the pigment had precipitated. Still liquid crystal E-8 (biphenyl liquid crystal product name manufactured by BDH), 90
Although heated to ℃, the liquid crystal was hardly colored.

Next, 1 g of the same dye was uniformly mixed with a polyethylene terephthalate resin pellet 1 Kp having an intrinsic viscosity of 0.7, and 28
It was melt-extruded at 0°C and formed into a film.

The film was stretched 5 times in the longitudinal direction using a roll stretching machine to obtain a film-like test piece with a thickness of 80 μm. Maximum absorption wavelength 520
The dichroic ratio of the dye in nm was 12.3. Example 2 2 g of the dye of Example 1 was added to polyethylene terephthalate resin pellets 1 Kp, mixed uniformly, and then melt-extruded to form a film of about 200 μm. This film was stretched 5 times in the horizontal direction at 80°C using a tenter stretching machine, and
Heat treatment was performed at 50°C for 1 minute.

A clear red polarizing film is obtained, with a maximum absorption wavelength of 520
The degree of polarization in nm was excellent at 91%. This polarizing film was heated to 500°C under conditions of 80°C and 90% relative humidity.
Although it was left for a long time, there was no substantial change in hue or decrease in the degree of polarization.Also, the shrinkage rate of the film was less than 1% in both the vertical and horizontal directions, and it had good dimensional stability. was.

Example 3 (Table 1, dye synthesis of dye number 5) Piphenyl-4'-(naphthalene-2,3-dicarboximide)-4 was used instead of piphenyl-4,4'-dicarboxylic acid monochloride in Example 1. -A reddish-purple powder dye (Table 1, dye number 5, m, p, >300°C) was obtained in the same manner except that -carboxylic acid chloride was used.

- This dye is also almost insoluble in nitrobenzene and liquid crystal E-8, and the dichroic ratio of the dye in polyethylene terephthalate measured in the same manner as in Example 1 is 11.
．． 2 (maximum absorption wavelength 520 nm).

Example 4 Instead of the dye (number 1) in Example 2, Example 3
A bright red polarizing film was obtained in the same manner except that the dye was used. The degree of polarization is 90% (maximum absorption wavelength s2on
m), and as a result of the durability test, substantially no decrease in the degree of polarization was observed, and it had good dimensional stability.

Example 5 (Table 1, dye synthesis of dye number 21) 3-amino-1,2,5-trihydroxy-4,8-dinitroanthraquinone 15. ! ? , 18.9 g of 4'-(5'-methyl-benzoxasilyl)-piphenyl-4-carboxylic acid chloride and 1 g of zinc chloride were added in 3007 rL of nitrobenzene at 70°C for 1 hour (218
After reacting at 0°C for 10 hours, it was cooled and diluted with methanol 10
011Ll was added and the precipitate was filtered and washed with methanol and water. 1000 d of ethanol was added to the obtained r mass.
200 g of an aqueous solution containing 24.3 y of 60% sodium sulfide was added thereto, stirred under reflux for 10 hours, filtered while hot, washed with methanol and water, and dried. 17.6 g of crude dye was obtained. After pulverization, soluble impurities were removed by Soxhlet extraction using acetone, and a dark blue powdered pigment (Table 1, pigment number 21, m, p, > 3
00°C) was obtained. This dye is also almost insoluble in N,N-dimethylformamide and liquid crystal 2L r-1840 (trade name of phenylcyclohexane liquid crystal manufactured by Merck), and the two-color ratio in polyethylene terephthalate is 1.
2.1 (maximum absorption wavelength 615 nm).

Example 6 A bright blue polarizing film was obtained in the same manner except that the dye of Example 5 was used instead of the dye (number 1) in Example 2. The degree of polarization is 91%, and as a result of the durability test,
Substantially no decrease in the degree of polarization was observed, and it had good dimensional stability.

Example 7 (Table 1, dye synthesis of dye number 27) 1.4-diamino-anthraquinone-6-carboxylic acid chloride 15.9 of 1,9,3-amino-1,2-dihydroxyanthraquinone was added to 300 ml of nitrobenzene.
After cooling, the mixture was heated at 140° C. for 2 hours, filtered, washed with nitrobenzene, methanol, and water, and the mass f was dried. This was dissolved in 90% sulfuric acid 6009 at 105℃ for 5 minutes.
After stirring for an hour, drain into 500 mA of ice water, filter, and wash with 70% sulfuric acid.
! After boiling, cooling, filtering, washing with water, and drying, a dark purple crystalline dye (Table 1, dye number 27, m, p, > 3
00°C) was obtained. The dye is nitrobenzene and liquid crystal E-
The dichroic ratio in polyethylene terephthalate was 9.3 (maximum absorption wavelength 650 nm).

Example 8 A green polarizing film was obtained in the same manner as in Example 2, except that the dye of Example 7 was used instead of the dye (number 1) and nylon 6 was used instead of polyethylene terephthalate. The degree of polarization is 80% (maximum absorption wavelength 655 nm)
)Met.

Examples 9 to 34 Table 2 shows the dichroic ratios, polarization degrees, and hues of the colored polyethylene terephthalate films of the other dyes in Table 1.

Table 2 (Note) Winter polarizing film base polymer is unmarked: Polyethylene terephthalate 1): Ho! Mixture of 80% by weight of J ethylene terephthalate and 20% by weight of polybutylene terephthalate 2): Ho! Mixture of 80% by weight of J ethylene terephthalate and 20% by weight of polybutylene terephthalate 3): Comparative example 1 of polarization degree of a polarizing film which is nylon 6 Dichroic dye for liquid crystal (structure A blue polarizing film was obtained in the same manner as H, N OOH except that formula A: dichroic ratio 8) in polyethylene terephthalate was used. Maximum absorption wavelength 640nm
The degree of polarization at i2 was as low as 52%. However, in the manufacturing process of this film, when the heat treatment step after stretching was omitted, the degree of polarization was 78% at the same wavelength, and it was clear that the degree of polarization was significantly reduced in the heat treatment step. Also,
The shrinkage rate of the film after heat treatment was less than 1% in both the vertical and horizontal directions, whereas the film without heat treatment showed large shrinkage rates of 8% in the vertical direction and 15% in the horizontal direction, and lacked dimensional stability. .

The solubility of dye A in liquid crystal E-8 (trade name of nematic liquid crystal manufactured by BDH) is about 2.0% by weight.

Comparative Example 2 A red-orange polarizing film was obtained in the same manner as in Example 2, except that a dichroic dye for liquid crystals (structural formula B: dichroic ratio in polyethylene terephthalate: 8) was used instead of dye (1).

The degree of polarization at the maximum absorption wavelength of 495 nm was as low as 47%. However, although the degree of polarization of the immaturely processed film was as high as 80%, the shrinkage rate was 6% in the vertical direction and 12% in the horizontal direction, and it lacked dimensional stability.

The solubility of dye B in liquid crystal E-8 and nitrobenzene was about 1.0% by weight and about 0.6% by weight, respectively.

Comparative Example 3 Instead of dye (1) in Example 2, the following structural formula C
A polarizing film was prepared in the same manner except that dichroic dyes for liquid crystals of (2 color ratio in polyethylene terephthalate 7.5) and D (2' color ratio 8.0) were used.

NHl This polarizing film and the polarizing films of Examples 2 and 6 were heated in an open environment at 120° C. for 1000 hours. The degree of polarization of each polarizing film before and after the heating test is shown in Table 3, and the polarizing films using the dyes of Example 2 and Example 6 (numbers 1 and 21) are more stable than the comparative dyes C and D. It showed a polarizing property.

The solubility of C and D in liquid crystal E-8 was 1.0% by weight and 1.0% by weight, respectively.

Claims (2)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formula (I), Y is an oxygen atom or a sulfur atom,
X_1, X_2, X_3, X_4, X_5 and X_6
is a hydrogen atom, a halogen atom, a hydroxy group, or an amino group which may be substituted with an alkyl group having 1 to 3 carbon atoms, and Q is a formula (II), ▲A mathematical formula, a chemical formula, a table, etc.▼ or a formula (III), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ It is a monovalent group represented by. Here, in formula (II), R_
1 and R_2 are hydrogen atoms, halogen atoms, methyl groups or methoxy groups, m is an integer of 1, 2 or 3, and R_3 is -COOH, -COOR_4, -CO
NH_2, -CONHR_4, -OOCR_4, -NH
COR_4, -N=N-R_4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here R_
4 and ring A are R_1, R_2, -COOH and/or -COOC
A phenyl group, a biphenyl group, or a naphthalene group which may be substituted with an H_3 group. In formula (III), X_7
, X_8, X_9, X_1_0, X_1_1, X_1_
2 and X_1_3 are amino groups optionally substituted with a hydrogen atom, a halogen atom, a hydroxy group, or an alkyl group having 1 to 3 carbon atoms. When X_7 is an amino group or X_7 and X_9 are both amino groups, X_
1, X_2, X_3, X_4, X_5, X_6, X_8
, X_9, X_1_0, X_1_1, X_1_2 and X_1_3 are not hydrogen atoms at the same time]. (2) In the hydrophobic polymer, there are general formulas (I) ▲mathematical formulas, chemical formulas, tables, etc.▼(I) [In formula (I), Y is an oxygen atom or a sulfur atom,
X_1, X_2, X_3, X_4, X_5 and X_6
is an amino group that may be substituted with a hydrogen atom, a halogen atom, a hydroxy group, or an alkyl group having 1 to 3 carbon atoms, and Q is the formula (II), ▲ Numerical formula, chemical formula, table, etc. ▼ (II) or formula (III), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) It is a monovalent group represented by. Here, in formula (II), R_
1 and R_2 are a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, m is an integer of 1, 2, or 3, and R_3 is -COOH, -COOR_4, -C
ONH_2, -CONHR_4, -OOCR_4, -N
HCOR_4, -N=N-R_4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here R_
4 and ring A are R_1, R_2, -COOH and/or -COOC
A phenyl group, a biphenyl group, or a naphthalene group which may be substituted with an H_3 group. In formula (III), X_7
, X_8, X_9, X_1_0, X_1_1, X_1_
2 and X_1_3 are amino groups optionally substituted with a hydrogen atom, a halogen atom, a hydroxy group, or an alkyl group having 1 to 3 carbon atoms. Here, when X_7 is an amino group or X_7 and X_9 are both amino groups,
_1, X_2, X_3, X_4, X_5, X_6, X_
8.X_9,