JPS6349705A - Polarizing film - Google Patents

Abstract

PURPOSE:To improve the polarization performance, weatherability, transparency, etc., of a polarizing film by incorporating a specific quinophthalone compd. into a film base material. CONSTITUTION:The quinophthalone compd. expressed by the formula I is incorporated into the film base material (e.g.: liquid crystalline polyester). In the formula, Y denotes the formula II or III; R<1> denotes H, (alkoxy)alkyl, alkoxy, etc.,; R<2> denotes an (alkoxy)alkyl, aralkyl, aryl, etc. The compd. expressed by the formula I has the good compatibility with the polymer of the film base material and exhibits high dichromaticity. The polarizing film having the excellent polarization performance, heat resistance, moisture resistance, weatherability, and transparency is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a polarizing film containing a quinophthalone compound.

(Conventional technology) Conventional polarizing films include polyvinyl alcohol (
It is well known that a PV film is dyed with iodine or a dichroic dye. However, although these polarizing films have excellent polarizing performance, they have drawbacks in heat resistance and moisture resistance, and to improve this, films laminated with cellulose acetate films have been put into practical use. However, even this may not provide sufficient moisture resistance depending on the application.

As a polarizing film based on a hydrophobic polymer other than PTA, a secondary optical film is also being considered in which a vinyl halide polymer such as PVO or PVDC is dehydrohalogenated to form a polyene structure. However, these have not yet become mainstream in polarizing films because they have problems with heat resistance, stability against light and oxygen, and it is not possible to freely select the hue.

Furthermore, for example, Japanese Patent Publication Sho≠Ter 32 Kosan Publication, Japanese Patent Publication No. Sho J'
According to μm1as153, etc., a polyamide polarizing film is disclosed. However, polyamide dye-based polarizing film has better heat resistance, moisture resistance, mechanical strength, etc. than PVA.
- Superior to iodine polarizing film, PTA- dichroic dye polarizing film, and polyene polarizing film,
The polarization performance is inferior to the three.

(Problems to be Solved by the Invention) In view of the above-mentioned circumstances, the present inventors used an organic resin polymer as a film base material, and developed a method using quinophthalonite, which is well compatible with this polymer and has high dichroism. The present invention aims to provide a novel polarizing film having excellent properties such as polarization performance, heat resistance, moisture resistance, weather resistance, and transparency by incorporating such compounds.

(Means for Solving the Problems) The present invention is based on the following general formula (1). , an aryloxy group, a carboxylic acid ester group, a carboxylic acid amide group, or a cycloalkyl group, and R- represents an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group or a cycloalkyl group. In each group represented by the substituent R11R8, a ``ton'', a cycloalkyl ring, and an aryl ring may be left as ``ft''. ] A polarizing film characterized by containing a quinophthalone compound represented by:

In the quinophthalone compound represented by formula (1) of the present invention, the alkyl group represented by the substituent R includes a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, Examples of the alkoxyalkyl group represented by R1 and RZ include linear or branched alkyl groups such as a nonyl group, and straight-chain or branched alkyl groups such as a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, and a methoxyethyl group. Chain-like realkoxy7 alkyl groups are mentioned, and the alkoxy group represented by R1 includes ethoxy groups,
Straight chain or branched alkoxy groups such as propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, nonyloxy group, etc. are mentioned, and examples of the alkoxyalkoxy group represented by R1 include methoxyethoxy group, Examples include straight chain or branched alkoxyalkoxy groups such as ethoxyethoxy group and methoxypropoxy group.

The number of carbon atoms in the above alkyl group, alkoxyalkyl group, alkoxy group, and alkoxyalkoxy group is /~//
Among these, a carbon number of / to 2 is preferred.

As the aralkyl group represented by substituents R1 and RZ,
Benzyl groups, 7enethyl groups, etc. are preferable, and specifically, p-ethylbenzyl group, p-butylbenzyl group, p-
-butylphenethyl group, p-hexylphenethyl group, p
-7') Aralkyl groups substituted with linear or branched alkyl groups or alkoxy groups such as xybenzyl group and p-butoxy7enether group.

As the aralkyloxy group represented by substituent R1,
Examples include aralkyloxy groups having the above-mentioned aralkyl groups.

The aryl group represented by fit, radicals R1 and R2 is preferably a phenyl group, and may be substituted with an @ chain or branched alkyl group or alkoxy group.

Furthermore, the phenyl groups may be substituted with an aralkyl group, an aralkyloxy group, a carboxylic acid ester group, a carboxylic acid amide group, a cycloalkyl group, or an aryl group, and these substituents are linear or branched alkyl groups. It may be substituted with a group or an alkoxy group.

Specifically, phenyl group, p-ethylphenyl group, p-
butylphenyl group, p-octylphenyl group, p-propyloxyphenyl group, p-butyloxyphenyl group,
p-hebutyloxyphenyl group, p-benzylphenyl f, p-7enethylphenyl group, p-butylphenethylphenyl group, p-benzyloxyphenyl group, p-butylpe/zyloxyphenyl group, p-hexylbenzyloxyphenyl group , phenoxycarbonylphenyl group, p
-butylphenoxycarbonylphenyl group, p-octylphenoxycarbonylphenyl group, p-butylcyclohexyloxycarbonylphenyl group, p-benzoyloxyphenyl group sp -(p' -)f rubenzoyloxy)phenyl group% p-benzoylamino Phenyl group, p-(p'-butylbenzoylamino)phenyl group, anilinocarbonylphenyl group, p-7'' tylanilinocarbonylphenyl group, p-octyloxyanilinocarbonylphenyl group, cyclohexylaminocarbonylphenyl group, ≠ -phthylcyclohexylaminocarbonylphenyl group, Hiro-cyclohexylphenyl group, Hiro-(Hiro-butylcyclohexylphenyl group, ≠-(≠-
hexylcyclohexyl) phenyl group, biphenyl group,
≠-Methylbi, etc. can be mentioned.

Examples of the arylox7 group represented by the substituent R1 include the above-mentioned aryloxy group having an aryl group.

As the carboxylic acid ester group represented by substituent 11,
phenyl ester, p-ethyl 7enyl ester, p-
Examples include phenyl esters which may be substituted with a linear or branched alkyl group or phenyl group, such as butylphenyl ester, p-hebutylphenyl ester, p-octyloxyphenyl ester, and biphenyl ester.

As an example of the carboxylic acid amide group represented by the substituent R1, a carboxylic acid anilide or an alkyl amide is preferable,
Specific examples include straight-chain or branched alkyl groups, alkoxy Examples thereof include anilides which may be substituted with groups or phenyl groups, and alkylamides such as N-n-butylamide and N-n-octylamide.

Examples of the cycloalkyl group represented by the substituents R1 and R2 include cyclopentyl algae, cyclohexyl threads, cycloheptyl groups, etc. Among these, the cyclohexyl group is preferable, and the cycloalkyl group is preferably substituted with a linear or branched alkyl group. It's okay.

Specifically, Hiro-propylcyclohexyl group, Hiro-butylcyclohexyl group, ≠-pentylcyclohexyl group,
Examples include Hiro-hexylcyclohexyl group, ≠-hebutylcyclohexyl group, Hiro-octylfuclohexyl group, and the like.

The quinophthalone compound represented by the general formula (1) of the present invention can be synthesized by a known method.

As a typical example, the following general formula (II) (wherein R1 is the same as the front leg general formula (1)) is reacted with naphthalene anhydride, 3-dicarboxylic acid, or pyromellitic anhydride to form the following general formula, R1 is the general formula (1) shown above.
represents the same group. ), and in the above general formula (In), Y' is NH, -R''...song...
The compound of general formula (1) can be obtained by reacting an amine derivative represented by CF/).

The polarizing film of the present invention can be produced by adding the quinophthalone compound to a film base material.

Examples of organic resin polymers used as the film base material of the present invention include polyesters, polycarbonates, polyethersulfones, polyimides, polyamides, 10genated vinyl polymers, halogenated vinylidene polymers, and polyvinyl alcohol. Examples include ethylene-vinyl acetate copolymer systems, cellulose systems, polyvinyl butyral systems, and liquid crystalline polymer systems. Examples of liquid crystalline polymers include polyethylene terephthalate-parahydroxy-7benzoic acid copolyesters.

The polyethylene terephthalate-bara hydroxybenzoic acid copolymer polyester, which is a liquid crystalline polymer, contains a polyethylene terephthalate component (A) and a parahydroxybenzoic acid component (B), and the composition ratio of (A) to (B) is from 60 to 60. It is a polyester resin that is copolymerized so that the ratio is between There is.

Among these polymer systems, polyester systems, polyamide systems, polyimide systems, polyethylene terephthalate-parahydroxybenzoic acid copolymerized polyester liquid crystal polymer systems, etc., which have excellent heat resistance and moisture resistance, are preferred.

A quinophthalone compound, which is a dichroic dye of the present invention, is added to the film base material in an amount of 0.07 to 10*jk%.

Preferably 0. A polarizing film is manufactured by adding θj−j weight il:%.

The quinophthalone compounds of the present invention can be used as a mixture of two or more types, if necessary, and may also be used in combination with other dichroic dyes, non-dichroic dyes, ultraviolet absorbers, antioxidants, etc. It may be used with the addition of additives.

The polarizing film of the present invention is usually produced by melting and homogenizing a composition consisting of an organic resin polymer, a quinophthalone compound, etc., which is the film base material, and forming the film or sheet into a film or sheet. - 7 seconds to 3 at 700 to 2jθ℃ after elongation by 3 to 7.2 times in the axial direction
For example, a film with a thickness of 30 to -00 μm can be produced by heat treatment for 0 minutes, but if necessary,
It may be stretched in a direction perpendicular to the main stretching direction.

When producing a polarizing film from the above-mentioned liquid crystalline polyester resin, the resin is mixed with a dichroic dye, and then melted and formed into a film using a rectangular or circular die under moderate shear and draft conditions. 'ru.

The higher the shear rate, the better, and the general film forming conditions (
Shearing rate: several tens of 6θC-1 to several hundred 5ea-') can provide sufficient orientation and transparency, but the shearing rate of /θ00
By forming the film under high shear of sec or more, the orientation and transparency are further improved.

The thickness of the manufactured film is usually set to 700 μm or less in order to impart transparency.

The polarizing 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 prosthetic layer may be formed by laminating with a polymer such as triacetate, acrylic, or urethane, or by vapor deposition, sputtering, or A transparent conductive film of indium-tin oxide or the like is formed by a coating method and put into practical use.

(Examples) Hereinafter, the present invention will be explained by examples, but the present invention is not limited to the following examples.

In the examples, the dye orientation number (Fdye) of the quinophthalone compound, which is a dichroic dye, was calculated by the following method.

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

D -Log (Io/1m)/Log (1°/11)...(2) However, the transmittance of the undyed film under the same stretching conditions and the same treatment is Io, and the polarization plane of the incident light is and the transmittance values when the stretching axis is straight and parallel, respectively■! , II. The Fdye value represents the degree of orientation of the dichroic dye, and a higher IPdye value indicates a higher polarizing performance of the polarizing film.

Example / Polyethylene terephthalate oligomer (ηinh θ
, /Odl/f) /θθ'lE9 parts rose hydroxybenzoic acid-2? ! Parts by weight and 73 parts by weight of 7th tin acetate θ were stirred at 220°C for an hour under a nitrogen stream, and then after the temperature was lowered to /4c0°C, 246 parts by weight of acetic anhydride was added.
The mixture was stirred for 30 minutes.

Without allowing acetic acid to distill out, the temperature was raised to 2J°C, and after adding 0.23 parts by weight of zinc acetate dihydrate, the mixture was heated to 0, J torr.
Gradually reduce the pressure at t for g time t? r,L polymerization was completed.

The composition of the obtained polymer is 2θmolti polyethylene terephthalate component and parahydroxybenzoic acid component? It was confirmed that it was a θ morch and exhibited anisotropy when melted under a polarizing microscope furnace equipped with a heat stage.

This liquid crystalline polyester resin was diced into T-dies (die width/2
Ofell; lip clearance 0.1rtvn)
A film was formed using a JOWM extruder equipped with. At this time, the temperature was -27J℃, the shear rate was 200Se
c-', draft ratio/! The test was carried out using an air gap ttorNn water cooling system using a cooling water tank.

Next, 15t of a quinophthalone compound represented by the following formula was mixed with the above liquid crystalline polyester resin Jjc9 using a Henschel mixer, and T-die film formation was performed in the same manner as above to form a yellow-colored polarizing film with a thickness of 70 μm. Manufactured.

The maximum absorption wavelength of this polarized light) f lume was Hirossnm, and Fdye was θ, 7.

The above quinophthalone compound was synthesized as follows.

The compound φ, -ta and Hiro-n-butylcyclohexylamine 8≦f in nitrobenzene jOd at /40°C to /7
Heat and stir at 0°C for 5 hours. After the reaction was completed, the mixture was cooled to jθ°C, methanol was added, and the precipitated crystals were collected and dried to obtain the quinophthalone compound≠Of used in this example.

The melting point was -32 to C3/°C.

EXAMPLE Copolyethylene terephthalate resin/copolyethylene terephthalate resin/quinophthalone compound/f produced in Example/ was melt-mixed at 210° C. to form a film to obtain a film colored bright yellow.

This film was stretched 5 times in the uniaxial direction at 0° C. using a stretching machine manufactured by Long Co., Ltd. to obtain a yellow polarizing film with a thickness of 700 μm.

The maximum absorption wavelength of this polarizing film is ≠! , 3 nm, Fdye was 0.1 $.

Example 3 Liquid crystalline polyester resin 3 prepared in Example 3, compound of general formula (II) with R1=H, and anhydrous naphthalene-λ
, a quinophthalone compound represented by the following formula synthesized using 3-dicarboxylic acid/It and Example/
A yellow colored polarizing film was produced in the same manner as above.

The maximum absorption wavelength of this polarizing film is 4 cd! nm,
Fdye is 0.2! Met.

Example ≠ A polarizing film was manufactured using the quinophthalone compounds shown in Tables 1 and 2 below in the same manner as in Example 1 using the liquid crystalline polyester resin manufactured in Example 1. The maximum absorption wavelength and Fd7θ value are shown in Tables 1 and 2.

Table 2 Table 1 (Effects of the Invention) The quinophthalone compound contained in the polarizing film of the present invention is well compatible with the organic resin polymer of the film base material and has high dichroism. According to the present invention, a polarizing film excellent in all of polarizing performance, heat resistance, moisture resistance, weather resistance, and transparency can be obtained.

Claims (1)

[Claims] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The expression R^1 is a hydrogen atom, an alkyl group, an alkoxyalkyl group, an alkoxy group, an alkoxyalkoxy group,
It represents an aralkyl group, an aralkyloxy group, an aryl group, an aryloxy group, a carboxylic acid ester group, a carboxylic acid amide group, or a cycloalkyl group, and R^2 is an alkyl group, an alkoxyalkyl group, an aralkyl group, an aryl group, or a cycloalkyl group. Represents an alkyl group. Substituent R^1
, R^2, the cycloalkyl ring and aryl ring may be substituted. ] A polarizing film characterized by containing a quinophthalone compound represented by: