JPS63174969A - Anthraquinone based compound and polarizing film using said compound - Google Patents

Abstract

NEW MATERIAL:An anthraquinone based compound expressed by formula I [R is -NHCOR<1>, -CONHR<1> (R<1> is alkyl, aryl or cycloalkyl which may have a substituent group) of formula II (A is aromatic or aliphatic ring which may be substituted)]. USE:A film substrate capable of providing polarizing performances and characteristics of heat, moisture, weather resistance, transparency, etc. PREPARATION:For example, 1,5-bis(4'-aminophenylthio)anthraquinone is reacted with a compound expressed by formula III (X is halogen) or formula IV in an aromatic or amide based solvent to afford the aimed compound expressed by formula I. A deacidifying agent, e.g. triethylamine, potassium carbonate, etc., may be used in reacting the compound expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel anthraquinone compound and a polarizing film containing the same.

[Conventional technology]

As a conventional polarizing film, a polyvinyl alcohol (PV, A) film dyed with iodine or a dichroic dye is well known. However, although these polarizing films have excellent polarizing performance, they have drawbacks in heat resistance, moisture resistance, etc., and in order to improve these problems, they have been put into practical use after being laminated with a cellulose acetate film or the like. However, even this does not provide sufficient moisture resistance depending on the application.

As a polarizing film based on a hydrophobic polymer other than PvA, a polarizing film in which a polyene structure is formed by de-hydrogenation treatment of a norodanated vinyl polymer such as PVC or PVVC is also being considered. These also have problems with heat resistance and stability against light and oxygen, and because it is impossible to freely select the hue, they have not yet become mainstream in polarizing films.

Furthermore, for example, Japanese Patent Publication No. 311, Japanese Patent Application Publication No. 5, No.
Hiro! According to Publication No. /j3, etc., a polyamide polarizing film is disclosed. However, polyamide dye-based polarizing film has poor heat resistance, moisture resistance, mechanical strength, etc.
- Superior to iodine polarizing film, PTA- dichroic dye polarizing film, and polyene polarizing film,
The polarization performance is inferior to these three.

[Problem that the invention seeks to solve]

The present invention provides a novel anthraquinone compound that is well compatible with organic resin polymers and has high dichroism, and also provides excellent polarizing performance by incorporating this compound into film 1; an organic resin polymer as a base material. The present invention also provides a novel polarizing film having properties such as heat resistance, moisture resistance, weather resistance, and transparency.

[Means for solving problems]

The present invention relates to general formula CI) general formula (1) (wherein, R is -NTlIC!ORI, -CONHR
I i represents an aryl group or cycloalkyl group which may have a substituent, and ring represents an aromatic ring or aliphatic ring which may be substituted. ) and a polarizing film characterized by containing the anthraquinone compound.

Next, the structure of the anthraquinone compound represented by the general formula (1) of the present invention will be explained in detail.

The substituent R is -NH(!ORI, -0ONHRI
t 7'hti preferably represents a straight or branched alkyl group having carbon atoms/~r. Furthermore, examples of the aryl group which may have a substituent include a phenyl group; an alkyl group, preferably having carbon atoms/~? Phenyl group substituted with an alkyl group; alkoxy group, preferably carbon number/-
A phenyl group substituted with an alkoxy group of Or a phenyl group substituted with an arylcarbonylamino group such as benzoylamino, p-butylbenzoylamino or p-phenylbenzoylamine; Hiro-cyclohexylphenyl group; trans-≠-alkyl, preferably carbon number/? Examples include an alkyl group-substituted cyclohexyl phenyl group.

Furthermore, examples of the cycloalkyl group which may have a substituent include a cyclohexyl group, a ≠-alkylcyclohexyl group, and preferably a trans-7≠-alkyl group substituted with an alkyl having a carbon number of 1 to 1. Examples include a cyclohexyl group and a cyclohexyl group.

X is a chlorine atom, a bromine atom, a bromine atom, (R3
It represents an alkyl group, and an alkyl group having carbon number/♂ is preferable. ), -〇〇N1'IR" 1-Coo+R4(
R4 is a hydrogen atom, an alkoxy group with carbon number /-/, and the next is R
3 is shown. ), cyclic imides include aliphatic cyclic imides.

The anthraquinone compound represented by the general formula (1) of the invention is, for example, /,! -bis(Hiro'-aminophenylthio)anthraquinone in an aromatic solvent such as monochlorobenzene, dichlorobenzene, F')chlorobenzene, nitrobenzene, or N,N-dimethylformamide, N
- In amide solvents such as methylacetamide and N-methylpyrrolidone, for example! At a temperature of θ to 200'C, the following general formula (II) or (II) , represents a halogen atom such as a chlorine atom, a bromine atom, etc.) (wherein, ring A has the same meaning as in general formula (1)).

In addition, when the above general formula (It) is reacted.

Alkylamine deoxidizers such as triethylamine and tributylamine; nitrogen-containing aromatic deoxidizers such as pyridine, picoline, quinoline, and quinaldine.

potassium carbonate, sodium carbonate, sodium bicarbonate,
Inorganic deoxidizing agents such as potassium hydroxide may also be used.

In addition, the anthraquinone compound represented by the general formula (1) is /, Jr-dichloroanthraquino y and the following general formula (I
IV) (wherein, R has the same meaning as in general formula CI).

) in an amide solvent such as N,N-dimethylformamide, N-methylacetamide, N-methylpyrrolidone,
In the presence of the aforementioned deoxidizer! 4 can be obtained by reacting at a temperature of 0 to xoo°C.

Examples of the organic resin used as the film base material of the polarizing film of the present invention include polyester-based, polycarbonate-based, polyethersulfone-based, polyimide-based, polyamide-based, halogenated vinyl polymer system, halogenated vinylidene polymer system, Examples include polyvinyl alcohol, ethylene-vinyl acetate copolymer, cellulose, polyvinyl butyral, and liquid crystal polymer. Examples of liquid crystalline polymers include polyethylene terephthalate-parahydroxybenzoic acid copolyesters, and the like.

Among these polymers, polyesters such as polyethylene terephthalate and polyethylene naphthalate, which have excellent heat resistance and moisture resistance, polyamides, polyimides, and polyethylene terephthalate-halahydrocarbon 7
An, l? Acid copolymerized polyester liquid crystalline polymers and the like are preferred.

The dichroic dye of the present invention, which has the general formula (
1) Anthraquinone compounds represented by 0007-
A polarizing film is produced by adding 70% by weight, preferably 0.01 to 31% by weight.

The anthraquinone compound of the present invention can be used in combination of two or more types as required, and can be used in combination with other dichroic dyes, non-dichroic dyes, ultraviolet absorbers, antioxidants, etc. Additives may be added.

The method for manufacturing the polarizing film of the present invention is not particularly limited, and usually involves melting and homogenizing a composition consisting of these film base materials, an anthraquinone compound as a dichroic dye, and various additives, and forming it into a film or sheet. and then 2
A film with a thickness of, for example, 30 to 2Qθμm is produced by stretching the film 3 to 72 times in the −axial direction under a temperature condition of 0 to 20σ℃, and then heat treating it at 10′0−Iθ℃ for 1 second to 30 minutes. However, if necessary, it may be stretched in a direction perpendicular to the main stretching direction.

The nine-light film produced in this way can be used after being subjected to various processing. For example, in addition to being used as a film or sheet, depending on the purpose of use, a protective layer may be formed by laminating with a polymer such as triacetate, acrylic, or urethane, or by vapor deposition, sputtering, or coating on the surface of the polarizing film. , a transparent conductive film of indium-tin oxide, etc. is formed and put to practical use.

〔Example〕

The present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these in any way.

In addition, in the following examples, the dye orientation system number (Fdye) of the anthraquinone compound which is the dichroic dye of the present invention
was calculated by the following method.

IPdye = (D-/)/CD+J)
(1) Here, D is the absorption co-color ratio of the dichroic dye-containing film and is based on the following formula (2).

D = Log(lo/In)/Log(io/
(2) However, if the transmittance of an undyed film under the same processing conditions is 10,
Let IllIm be the transmittance value when the polarization plane of the incident light beam and the stretching axis are perpendicular and parallel, respectively. The Fc1ye value represents the degree of orientation of the dichroic dye, and a higher %F'dye value indicates a higher polarizing performance of the polarizing film.

Example/Anthraquinone compound/f represented by the following formula was melt-mixed with polyethylene naphthalate resin/14 at 300° C. and molded to obtain a film colored in bright yellow.

This film was uniaxially stretched 5 times at θ° C. using a stretching machine manufactured by Long Co., Ltd. to obtain a yellow polarizing film with a thickness of 700 μm.

What is the maximum absorption wavelength of this polarizing film? nm, and Fdye is 0. ? It was ≠.

The above anthraquinone compound was synthesized as follows.

/,! -bis(≠'-aminophenylthio)anthraquinone/f, naphthalene-2,3-dicarboxylic anhydride θ
,! 7t and N,N-dimethylformamide! The mixture of θd is 7! After heating and stirring at 0°C for an hour, and cooling, the precipitate was filtered, washed with methanol and dried, and the following anthraquinone compound θ, ? I got 7f. The melting point is 3θO℃ or higher.

Example λ Polyethylene naphthalate resin/1f was melt-mixed at 300°C with an anthraquinone compound represented by the following formula for 'i' to form a film, which was colored bright yellow to obtain a film.

This film was used and stretched in the same manner as in Example to obtain a yellow polarizing film with a thickness of 700 μm.

The maximum absorption wavelength of this polarizing film is 4Cjjz[l, and Fc1yθ is 0. /! Atatsu nine.

The above anthraquinone compound was synthesized as follows.

/, j-bis(4c/-aminophenylthio)anthraquinone/l at 7.30°C with monochlorobenzene/θ0-
≠-n-butoxybenzoic acid/,02
f ≠-n-butycupenzoyl chloride synthesized by reacting with 0.77 td of t-thionyl was added, and further pyridine/, 71ff/ was added to give 130
React at ℃ for 3 hours. Cooling ridge, methanol 100r
xlf was added and the precipitated crystals were passed through to obtain 0.7at of the anthraquinone compound used in this example. Melting point is 30
Don't worry if it's over 0℃.

Example 3 Example 71 The following is the same as Example λ a! Anthraquinone compounds shown in Table 1 below were produced by the following operations, and a polarizing film was produced using them. What is its maximum absorption wavelength? (The values of 17e are also shown in Table 1.

〔Effect of the invention〕

Since the anthraquinone compound of the present invention is well compatible with the organic resin polymer of the film base material and has high dichroism, the polarizing film of the present invention has excellent polarization performance, heat resistance, moisture resistance, and weather resistance. Excellent in terms of transparency and transparency.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - (1 other person)

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] (In the formula, R represents -NHCOR^1, -CONHR^1 or ▲There are numerical formulas, chemical formulas, tables, etc.▼.However, R
^1 represents an alkyl group, an aryl group which may have a substituent, or a cycloalkyl group, and Ring A represents an optionally substituted aromatic ring or aliphatic ring. ) is an anthraquinone compound represented by (2) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
[I] (In the formula, R represents -NHCOR^1, -CONHR^1 or ▲There are numerical formulas, chemical formulas, tables, etc.▼.However, R
^1 represents an alkyl group, an aryl group which may have a substituent, or a cycloalkyl group, and Ring A represents an optionally substituted aromatic ring or aliphatic ring. ) A polarizing film characterized by containing an anthraquinone compound represented by: