JP3118100B2 - Quinophthalone compounds and colorants for liquid crystal materials and organic polymer materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quinophthalone compound useful for coloring a liquid crystal material or an organic polymer material. The present invention also relates to a colorant for a liquid crystal material and an organic polymer material.

[0002]

2. Description of the Related Art Conventionally, the following general formula

[0003]

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(Wherein, R is an alkoxy group, an alkylamino group, or an aralkyloxy group, and n is an integer of 1 to 8). It is known to color. (For example, Japanese Patent Publication No. 48-20476,
8-93778, JP-A-59-4674, JP-A-59-4674
-4675, JP-A-59-182877, JP-A-59-182877
However, when these compounds are used for coloring a liquid crystal material or an organic polymer material, they may not be used due to low compatibility with a liquid crystal compound, a solvent, a binder matrix and the like. For example,
When the compatibility with the liquid crystal compound is low, the contrast required for the guest-host type liquid crystal composition cannot be obtained.

When the solubility in a solvent is low, even if a dye / organic polymer coating film is formed by a solvent coating method, a coating film having a sufficient optical density cannot be obtained. When the compatibility with the binder matrix is low, the polymer film cannot be dyed at a high concentration,
Further, a film in which these known compounds are dispersed at a high concentration becomes opaque and cannot be used for applications requiring transparency such as a color filter.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have developed a quinophthalone derivative compound which has high solubility in liquid crystal materials and various resins and can be colored and dyed at a high concentration. As a result of diligent studies, they have found that a derivative having a heterocyclic ring is suitable for the purpose, and have made the present invention based on this finding.

Accordingly, an object of the present invention is to provide a high solvent solubility,
An object of the present invention is to provide a novel quinophthalone compound having high binder compatibility and stability against heat and light and suitable for coloring a liquid crystal material or an organic polymer material.

[0008]

The present invention for achieving the above object has the following general formula (1):

[0009]

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(R ₁ represents a hydrogen atom, an optionally branched alkyl group or a cycloalkyl group having 8 or less carbon atoms,
R ₂ represents a hydrogen atom, a p-tert-butylphenylthio group, and R ₃ represents a heterocyclic group shown below.

[0011]

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Wherein the hydrogen atom of the heterocyclic group is a branched alkyl group having 8 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, -CH ₂ OCOCH ₃ , -CH _{2
OCOCH 2 CH 3, -CH 2 OCOCH} 2 CH 2 CH 3, -
CH ₂ OCOCH ₂ CH ₂ CH ₂ CH ₃ may be substituted. However, when R ₁ is a cyclohexyl group, R ₂ may be a hydrogen atom and R ₃ may be the following heterocyclic group. )

[0013]

Embedded image And a quinophthalone compound represented by the formula:

Further, the present invention provides a compound represented by the following general formula (2):

[0015]

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(R ₁ represents a hydrogen atom, an optionally branched alkyl group or a cycloalkyl group having 8 or less carbon atoms,
R ₂ represents a hydrogen atom, a p-tert-butylphenylthio group, and R ₃ represents a heterocyclic group shown below.

[0017]

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Wherein the hydrogen atom of the heterocyclic group is an alkyl group having 8 or less carbon atoms which may be branched, an alkoxy group having 4 or less carbon atoms, --CH ₂ OCOCH ₃ , --CH ₂
OCOCH ₂ CH ₃ , —CH ₂ OCOCH (CH ₃ ) ₂ ,
_{CH 2 OCOCH 2 CH 2 CH 3} , -CH 2 OCOCH 2 CH
It may be substituted by ₂ CH ₂ CH ₃ . ) Are coloring agents for liquid crystal materials and organic polymer materials.

Hereinafter, the present invention will be described in detail.

In the quinophthalone compounds represented by the general formulas (1) and (2) which are the compounds of the present invention, R ₁
Represents a hydrogen atom, an optionally branched alkyl group having 8 or less carbon atoms, or a cycloalkyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, sec-butyl, tert-
Butyl, n-pentyl, n-hexyl, n-heptyl, n-
Octyl and the like can be exemplified.

The cycloalkyl group has 5 to 5 carbon atoms.
6 are preferable, and examples thereof include cyclopentyl and cyclohexyl.

R ₂ is a hydrogen atom or a p-tert-butylphenylthio group.

R ₃ is a substituted or unsubstituted heterocyclic group containing at least two or more atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom.

[0024]

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Wherein the hydrogen atom of the heterocyclic group is an alkyl group having 8 or less carbon atoms which may be branched, an alkoxy group having 4 or less carbon atoms, --CH ₂ OCOCH ₃ , --CH ₂
OCOC ₂ C ₅ , —CH ₂ OCOCH (CH ₃ ) ₂ , —CH ₂
OCOCH ₂ CH ₂ CH ₃ , —CH ₂ OCOCH ₂ CH ₂ CH
It may be substituted by ₂ CH ₃ .

Examples of the alkyl group which may be substituted with a hydrogen atom of the heterocyclic group and which may have 8 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Examples thereof include an n-butyl group, an iso-butyl group, a tert-butyl group, a hexyl group, and an octyl group. Examples of the alkoxy group having 4 or less carbon atoms include a methoxy group, an ethoxy group, and an n-butyl group.
-Propoxy group and n-butoxy group.

The quinophthalone compounds represented by the general formulas (1) and (2) of the present invention can be prepared, for example, by reacting a 3-hydroxy-2-methyl-4-cinchonic acid (a) and a phthalic anhydride ( b) to give quinophthalone (c), and the resulting quinophthalone (c)
In order to introduce a substituent at the position, the substituent may be replaced with a usual electrophilic reagent or may be once substituted with a halogen and then replaced with a usual nucleophile.

[0028]

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The reaction between the compound (a) and the compound (b) is carried out in a high boiling point solvent such as nitrobenzene, o-dichlorobenzene, sulfolane, DMF, DMI, etc.
It is carried out by heating to 230 ° C, preferably 180 to 210 ° C. In order to introduce the heterocyclic ring of R ₃ , a compound (c) in which a carboxylic acid or the like is introduced in accordance with the above reaction is used by using a compound in which a carboxylic acid has been introduced in advance at the substituent introduction position of the compound (b). After that, the desired compound can be obtained by a method such as cyclization.

In order to introduce a substituent at the 4-position of the obtained quinophthalone compound (c), the substituent may be replaced with a usual electrophilic reagent, or may be once substituted with halogen and replaced with a usual nucleophile.

The compound of the general formula (1) has a structure represented by the following general formula (1 ') as a tautomer, and this tautomer is also within the scope of right.

[0032]

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As a method of producing a liquid crystal composition using the quinophthalone compound of the present invention as a dye, a dye is dissolved in an appropriate liquid crystal compound, and a liquid crystal cell having a thickness of about 10 μm which has been treated in advance for homogenous alignment is prepared. What is necessary is just to enclose in. In this case, the amount of the dye to be added is usually 0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight, based on the liquid crystal. Commonly used liquid crystals include, for example, E
-8, E-7, E-44, ZLI-1132, ZLI-18
40, ZLI-2806 (Merck) and the like.
Further, the present dye is also useful for a PDLC type in which a solution of a dye dissolved in a liquid crystal compound is dispersed in a polymer matrix.

Further, as a method of coloring the resin using the present dye, the dye may be dissolved in a suitable synthetic resin at a temperature suitable for the resin, and then molded according to the intended use.
There is also a method of dyeing the already molded resin using an appropriate dyeing bath to which the present dye is added.

As resins generally used, PS, A
BS, PMMA, PC, PVC, PET, nylon 6, and the like. The amount of the dye added is 0.0
It is 1 to 10% by weight, preferably 0.01 to 5% by weight.

[0036]

The present invention will be described below in detail with reference to examples.
Parts in the examples indicate parts by weight, and% indicates% by weight.

Example 1 Method for producing compound of formula (B) 538 parts of sulfolane were added with 53.8 trimellitic anhydride.
And 50.8 parts of 3-hydroxy-2-methylquinoline-4-carboxylic acid were added, and the mixture was reacted at 200 ° C. for 1 hour to obtain 68 parts of a compound of the following formula (A) as a precursor of the target product.

[0038]

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10 parts of the compound of formula (A) and 0.4 pyridine
To 60 parts of o-dichlorobenzene and heated to 100 ° C., followed by addition of 7.2 parts of thionyl chloride.
For 2 hours. The excess thionyl chloride is then
Removed under reduced pressure at 00 ° C., and 3-amino-2-propanol
Add 4 parts and react at 100 ° C for 1 hour.
And reacted for 7 hours to obtain a compound of the following formula (B) 9.
5 parts were obtained.

[0040]

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The melting point was 244 to 246 ° C., and the maximum absorption wavelength in toluene was 448 nm.

[0042]

[Table 1]

Example 2 Preparation of the compound of the formula (C) 10 parts of the compound of the formula (A) and 0.4 part of pyridine are added to 50 parts of nitrobenzene, heated to 100 ° C. and subsequently 7.2 parts of thionyl chloride. Was added and reacted at 100 ° C. for 2 hours.
Thereafter, excess thionyl chloride was removed under reduced pressure at 100 ° C., and 4.6 parts of iso-propylcarbonylhydrazine was added and reacted for 1 hour. Further, 14.3 parts of thionyl chloride was added, and the mixture was heated at 130 ° C. and reacted for 4 hours to obtain 7.9 parts of a compound of the following formula (C).

[0044]

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The melting point was 210 to 211 ° C., and the maximum absorption wavelength in toluene was 450 nm.

[0046]

[Table 2]

Example 3 Method for producing compound of formula (E) Trimellitic anhydride 21.1 was added to 285 parts of sulfolane.
Then, the mixture was heated to 185 ° C., and 3-hydroxy-2-methyl-6-iso-propylquinoline-4-carboxylic acid was added.
6 parts were further added and reacted at 200 ° C. for 1 hour to obtain 37.2 parts of a compound of the following formula (D) which was a precursor of the target product.

[0048]

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6 parts of the compound of the formula (D) and 0.2 parts of pyridine are added to 42 parts of o-dichlorobenzene, heated to 100 ° C., and then 3.8 parts of thionyl chloride is added, followed by 2 hours at 100 ° C. Reacted. Thereafter, excess thionyl chloride was added to 10
Removed under reduced pressure at 0 ° C. Cool to 80 ° C and allow 2-amino-2
6.9 parts of 1-ethyl-1,3-propanediol was added to give 8
The reaction was performed at 0 ° C. for 2 hours. Then heat to 170 ° C,
The reaction was carried out for 5 hours to obtain 4.2 parts of a compound of the following formula (E).

[0050]

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The melting point was 239 to 241 ° C., and the maximum absorption wavelength in toluene was 450 nm.

[0052]

[Table 3]

Synthesis Example 1 Method for producing compound of formula (F) 4 parts of the compound of formula (E) were added to 40 parts of N-methylpyrrolidone, and 14 parts of isobutyric acid chloride were further added. The mixture was reacted at room temperature for 5 hours. There were obtained 4.4 parts of a compound of the following formula (F).

[0054]

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The melting point was 163-165 ° C., and the maximum absorption wavelength in toluene was 450 nm.

[0056]

[Table 4]

Examples 4 to 10 Table 1 below shows the structural formulas of the compounds of Examples 4 to 10 and the maximum absorption wavelength (λmax) and melting point thereof.

[0058]

[Table 5]

[0059]

[Table 6]

(Liquid Crystal Production Examples 1-2 and Comparative Production Examples 1-2) 0.2 parts of the respective dyes of Synthesis Example 1 and Example 5 were added to 9.8 parts of a liquid crystal mixture of Merck Co., Ltd. product code E-8. , About 6
After heating to 0 ° C. to completely dissolve and cool, it was sealed in a liquid crystal display device. This display device showed a clear dark yellow color when no voltage was applied, and only a colorless electrode portion when voltage was applied, showing good contrast.

This was placed in the optical path of a spectrophotometer, and the absorbance A measured by applying parallel linear polarization to the liquid crystal array and the absorbance A ′ measured by applying linear polarization perpendicular to the liquid crystal array were measured. The dichroic ratio was calculated from the ratio = A / A ′.

As a comparative production example, the following formula (G),
Liquid crystals similar to those described above were produced using the comparative compound represented by (H). The results are shown in Table-2.

[0063]

[Table 7]

* Since the compounds (G) and (H) were not completely dissolved in the liquid crystal, the dichroic ratio could not be calculated.

[0065]

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[0066]

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(Solubility Measurement Examples 1-4, Comparative Measurement Example 1,
2) The solubility in a solvent was measured using the four compounds of Examples 1 to 3 and Synthesis Example 1 and the compounds (G) and (H) for comparison. The results are shown in Table-3.

[0068]

[Table 8]

As is evident from Table 3, the product of the present invention had high solubility in various media.

(Resin Coloring Suitability Test Examples 1-4) Compounds (B, C, E, F) of Examples 1-3 and Synthesis Example 1
Table 4 shows the results of a resin coloring suitability test conducted using the above.

[0071]

[Table 9]

PS: polystyrene ABS: acrylonitrile-butadiene-styrene PET: polyethylene glycol-terephthalate PC: polycarbonate L: light resistance 63 ° C./80 hr carbon arc lamp blue scale judgment H: heat resistance 300 ° C./10 min gray scale Judgment B: Bleeding property: 5 kg of a colored plate superimposed on a PVC plate
/ Cm ² at 90 ° C for 5 hours, and then judge the contamination of the PVC board by gray scale. Lightfastness: Grade 7 or higher by blue scale judgment ◎, 5 to 7 ○ Heat resistance, bleeding resistance: Class 5 or higher in blue scale
◎ 3 ~ 5 ○

[0073]

The compound of the present invention is very suitable for high-concentration coloring of liquid crystal materials and organic polymer materials.

Further, a material which is stable to heat, light, moisture, chemicals, etc., and which is colored by using this compound can maintain a clear and transparent color tone and is extremely excellent in storage stability. It is.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-50-35241 (JP, A) JP-A-49-26382 (JP, A) JP-A-5-229268 (JP, A) JP-A-5-229268 333598 (JP, A) JP 48-10515 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 25/00 C07D 215/22 C09K 19/60 G02F 1/13 500 CA (STN)

Claims (3)

(57) [Claims] [Claim 1] The following general formula (1) (R ₁ represents a hydrogen atom, an optionally branched alkyl group or cycloalkyl group having 8 or less carbon atoms, R ₂ represents a hydrogen atom, a p-tert-butylphenylthio group, R ₃
Is the following heterocyclic group: And the hydrogen atoms of these heterocyclic groups are those having 8 carbon atoms.
Following optionally branched alkyl group, having 4 or less of the alkoxy group having a _{carbon, -CH 2 OCOCH 3, -CH 2} OCOCH 2 C
H ₃ , —CH ₂ OCOCH ₂ CH ₂ CH ₃ , —CH ₂ OCOC
It may be substituted with H ₂ CH ₂ CH ₂ CH ₃ . Where R
_{When 1} is a cyclohexyl group, R ₂ may be a hydrogen atom and R ₃ may be the following heterocyclic group. ) A quinophthalone compound represented by the formula: 2. The following general formula (2): (R ₁ represents a hydrogen atom, an optionally branched alkyl group or cycloalkyl group having 8 or less carbon atoms, R ₂ represents a hydrogen atom, a p-tert-butylphenylthio group, R ₃
Is the following heterocyclic group: And the hydrogen atoms of these heterocyclic groups are those having 8 carbon atoms.
Following optionally branched alkyl group, having 4 or less of the alkoxy group having a _{carbon, -CH 2 OCOCH 3, -CH 2} OCOCH 2 C
H ₃ , —CH ₂ OCOCH (CH ₃ ) ₂ , —CH ₂ OCOC
H ₂ CH ₂ CH ₃ and —CH ₂ OCOCH ₂ CH ₂ CH ₂ CH ₃ may be substituted. ). 3. The following general formula (2): (R ₁ represents a hydrogen atom, an optionally branched alkyl group or cycloalkyl group having 8 or less carbon atoms, R ₂ represents a hydrogen atom, a p-tert-butylphenylthio group, R ₃
Is the following heterocyclic group: And the hydrogen atoms of these heterocyclic groups are those having 8 carbon atoms.
Following optionally branched alkyl group, having 4 or less of the alkoxy group having a _{carbon, -CH 2 OCOCH 3, -CH 2} OCOCH 2 C
H ₃ , —CH ₂ OCOCH (CH ₃ ) ₂ , —CH ₂ OCOC
H ₂ CH ₂ CH ₃ and —CH ₂ OCOCH ₂ CH ₂ CH ₂ CH ₃ may be substituted. A) a coloring agent for an organic polymer material represented by