JP2001159713A - New micropattern polarizing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a micropattern polarizing device which does not require extremely high positioning accuracy such as lamination and which shows excellent partial alignment of a dichroic dye compound, and to establish a method of producing that device. SOLUTION: The polarizing device is produced by arranging dichroic molecules in a micropattern in a thin film layer of a liquid crystal polymer having optical active groups irradiated with linearly polarized light. The liquid crystal polymer compound having optical active groups causes changes in the alignment of the molecular axes of the optical active groups by irradiation with linearly polarized light. The aforementioned changes in the alignment of the molecular axes mean such a phenomenon that after the molecules absorb the energy of the linearly polarized light, the direction of the molecular axis changes into a specified direction according to the linearly polarized light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel high-polarization-rate micro-patterned polarizing element and a method for producing the same, and more particularly to a liquid crystal display element capable of stereoscopic viewing using micro-patterned polarizing elements having different polarization axes.

[0002]

2. Description of the Related Art There are conventionally known several polarization elements in which a plurality of polarization regions having different polarization transmission axis directions are formed in a pattern. For example, Japanese Patent Application Laid-Open No. 62-96905 discloses that a resist is coated on a stretched polyvinyl alcohol film and then patterned and exposed and developed to pattern the resist. There has been proposed a method of forming a polarized region having a desired pattern by dyeing with a dye. Sadeg M.
Faris from the 1991 Society of Infomation and Disp
In lay conflict, a resist is applied on a stretched dichroic polyvinyl alcohol film, patterned and dissolved and removed with an aqueous solution of caustic soda to obtain a patterned polarizing film, and two patterned polarizing films with orthogonal polarization axes are superimposed. A method of producing a polarizing element called μPol and using it for stereoscopic viewing has been announced (SID 91 DIGEST p84
0-843). Japanese Patent Application Laid-Open No. Hei 7-261024 discloses a method of irradiating a photo-alignment material thin film coated on a substrate with polarized light in a pattern, forming a dichroic dye solution on the thin film, and forming a polarized region having a desired pattern. Has been proposed. JP 9
JP-A-73015 proposes a micro-patterned polarizing element in which a substrate is coated with an alignment film of a fluororesin, a resist is applied on the substrate, patterning is performed, and a material containing a dichroic dye is deposited and formed. Japanese Patent Application Laid-Open No. H10-160932 proposes a polarizing element in which a plurality of polarizing pieces are attached to a base material with different polarizing transmission axes of adjacent ones. Japanese Patent Application Laid-Open No. 10-160933 discloses that a polarizing film disposed on a base material is partially cut with a dicer to form a strip or lattice-like partial polarizing member having a polarization transmission axis directed in one direction. A polarizing film is arranged in a direction in which the polarizing axes are different, and the polarizing film portion on the existing polarizing member is scraped off with a dicer, and a polarizing element having a plurality of polarizing transmission axes or a polarizing transmission axis of a partial polarizing member cut with a dicer is used. There has been proposed a polarizing element in which different ones are bonded.

On the other hand, various methods have been proposed for stereoscopic vision, and binocular stereoscopic vision utilizing polarized light is one of them. It is also called a polarized eyeglass system, in which the right eye and the left eye wear glasses using polarizing plates whose polarization axes are orthogonal to each other, and the images for the right eye and the left eye having binocular parallax make the polarization plane of the light orthogonal to each observer. In this method, left and right image information is distributed to the left and right eyes by a polarizing plate of the eyeglasses. In order to project images having different polarization directions in this method, a method of combining images formed by using two display devices or projection devices with a half mirror or a polarizing mirror is used.
In this case, the display device is expensive and is suitable for displaying a stereoscopic image to a large number of spectators, but has a problem that it is not suitable for a display for home use or for an office where a small number of people can view the image. Therefore, if a micro-pattern polarizing element whose polarization axes are orthogonal to each other in the same plane is used for a display device, it is possible to simultaneously display the right-eye image and the left-eye image on one display device, and the device price is low. It is suggested that you can do it.

[0004]

The conventionally known polarizing element in which a plurality of polarization regions having different polarization transmission axis directions are formed in a pattern has the following problems. JP 6
In the method of 2-96905, since the stretched PVA film is dyed to dye the stretched PVA film, the polarizing ability is lower than that of the method of stretching after ordinary dyeing, and the stretched PVA film swells and loses uniaxiality when developing and patterning the resist. As a result, there is a problem that a polarizing element having a satisfactory polarization rate cannot be obtained as a result.

[0005] Sadeg M. Faris is a member of the Society of Information a
nd Display Conferance (SID 91
(DIGEST p840-843, USP5327285), a resist is applied on a stretched dichroic polyvinyl alcohol film, and after patterning, the remaining polarizing element portion swells when dissolved and removed with an aqueous solution of caustic soda. However, there is a problem in that extremely high positioning accuracy is required when bonding two types of substrates that are orthogonal to each other.

In the method disclosed in Japanese Patent Application Laid-Open No. Hei 7-261024, a thin film of a photo-alignment material applied on a substrate is irradiated with polarized light in a pattern, and a dichroic dye solution is coated and aligned thereon. Ichimura related to Mol.Cryst.Liq.Crys
t., 1997, Vol.298, pp221-226, report the following. This oriented dye film is treated with an atomic force microscope (A
When observed by FM), a portion where the dye is uniformly oriented as shown in FIG. 1 (a) and a portion where no dye is present and where the dye is not aligned (crater) as shown in FIG. 1 (b) are observed. FIG.
The absorbances of the part (a) and the part (b) were measured with a microspectrophotometer, and it was found that the large number of craters reduced the uniformity of the entire dye film and made the polarizing ability insufficient. Was. When the present inventors calculate the dichroic ratio (DR) from the absorbances of the portions shown in FIGS. 1A and 1B, DR (a) ≒ 3
There was a large difference of 0, DR (b) ≒ 1.3, and DR = 5 to 6 in a wider area including these, which was not a satisfactory level for a display element. The dichroic ratio (D
The calculation of R) is as follows. DR = A‖ / A⊥A‖: Absorbance when the polarization axis is parallel to the molecular long axis of the alignment dye. A⊥: Absorbance when the polarization axis is perpendicular to the molecular long axis of the alignment dye.

In the method disclosed in Japanese Patent Application Laid-Open No. 9-73015,
A micropatterned polarizing element is formed by coating a substrate with a fluororesin alignment film, applying a resist on it, patterning and then depositing a material containing a dichroic dye to form a micropatterned polarizing element. It is because the orientation of the fluororesin alignment film is reduced by the influence of the resist film which remains thin on the surface even after the development or the influence of the development process, or the orientation of the dichroic dye material deposited on it is sufficient However, there is a problem that the polarization ability is insufficient.

In the method disclosed in Japanese Patent Application Laid-Open No. 10-160932, a polarizing element is formed by adhering a plurality of polarizing pieces to a substrate with different polarization transmission axes of adjacent ones,
There is a problem that an extremely high positioning accuracy is required when bonding a plurality of polarizing pieces. In the method disclosed in Japanese Patent Application Laid-Open No. H10-160933, a polarizing film disposed on a substrate is partially cut with a dicer to form a strip or a grid-like partial polarizing member having a polarization transmission axis directed in one direction. A polarizing film is arranged in a direction in which the polarizing axes are different from each other, and the polarizing film portion above the existing polarizing member is scraped off with a dicer, and a polarizing element having a plurality of polarization transmission axes or a partial polarizing member cut off with a dicer. Although polarizing elements are formed by bonding materials having different transmission axes, the process of shaping with a dicer requires extremely high precision or is extremely high when bonding a plurality of partial polarizing members having different polarization transmission axes. There is a problem that positioning accuracy is required.

From such a viewpoint, the present inventors provide a micro-patterned polarizing element which does not require extremely high positioning accuracy such as bonding and has excellent partial orientation of a dichroic dye compound, and a method for producing the same. The present inventors have conducted intensive studies for the purpose of doing so and arrived at the present invention. The present invention relates to a method disclosed in
The problem of the method disclosed in JP-A No. 4 (1993) -174, in which the occurrence of a portion (crater) in which a dye hardly exists and is not oriented is minimized as much as possible, and the orientation of the dichroic compound is increased as a whole to a practical level for display devices. The present invention relates to a polarizing element, a method for producing the same, and a liquid crystalline polymer thin film having a photoactive group suitable therefor.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies on a photoactive molecular layer more suitable for a micropatterned anisotropic arrangement of dichroic dye molecules, and found that a polyamide having a photoactive group bonded thereto. It has been found that liquid crystalline polycondensation polymers such as polyimide and polyester, liquid crystalline polyaddition reaction polymers such as polyurethane, and liquid crystalline polyvinyl cinnamate have excellent properties. In the present invention, when a liquid crystalline polymer thin film having a photoactive group is used as an alignment film, the number of craters as shown in FIG. 1 (b) is extremely small, and even if it is present, the size is much smaller. I found a surprising fact. As a result, the average dichroic ratio was remarkably increased, and it was found that a product practically usable for display devices could be manufactured.

That is, the present invention provides (1) a dichroic polymer having a liquid crystalline polymer thin film layer having a photoactive group on a substrate and a layer containing dichroic molecules in contact with the liquid crystalline polymer thin film layer. (2) a photoactive group selected from non-aromatic N = N, non-aromatic C = C, and non-aromatic C = N The polarizing element according to the above (1), which is a group containing at least one double bond, (3) the above (1) or (2), wherein the liquid crystalline polymer thin film is a polyamide, polyimide, polyester, or polyurethane resin thin film.
(4) The polarizing element according to (1) or (2), wherein the liquid crystalline polymer thin film is a polyvinyl cinnamate resin thin film, and (5) a dye in which the dichroic molecules have lyotropic liquid crystallinity. The above (1), (2), (3) or (4)
(6) The polarizing element according to (5), wherein the dye having lyotropic liquid crystallinity is a dye having a hydrophilic substituent, (7) the polarizing element according to (5), wherein the hydrophilic substituent is a sulfonic acid group, a carboxylic acid group, or an amino acid. (6) a liquid crystal polymer thin film having a photoactive group on a substrate, irradiating the thin film with linearly polarized light, and then applying two colors on the thin film. (9) The method for producing a polarizing element according to (8), wherein the irradiation of linearly polarized light is performed through a micropatterned mask. (10) The method for producing a polarizing element according to the above (8), wherein the irradiation of linearly polarized light is performed using a laser beam having a polarizing property. (11) A liquid crystalline polymer thin film having a photoactive group is formed on a substrate. , A micro-patterned Irradiated with linearly polarized light through the disk,
Then, after irradiating linearly polarized light having different polarization axes through another micro-patterned mask, a method of manufacturing a polarizing element in which dichroic molecules are arranged in a micro-pattern on the thin film, (12) a liquid crystal display device Wherein at least one of the upper and lower substrates facing each other is a substrate having the polarizing element according to any one of the above (1) to (7), and (13) a liquid crystal display having a photoactive group. Molecular thin film,
(14) The liquid crystalline polymer thin film according to the above (13), wherein the molecular axes of the photoactive groups are arranged in a predetermined direction in a micropattern, and (15) the molecular axes of the photoactive groups are lattice-like. (1) characterized in that they are arranged in a certain direction.
4) The liquid crystal polymer thin film according to the above.

A liquid crystalline polymer is a polymer that exhibits liquid crystallinity under certain conditions, and a polymer that exhibits so-called lyotropic liquid crystallinity in the presence of a solvent and a thermostat that exhibits a liquid crystal structure in a molten state without the presence of a solvent. A tropic liquid crystalline polymer is known. Generally, a liquid crystalline polymer has a layer in which molecular chains are highly oriented in a flow direction in a liquid crystal state, and a high strength and high elastic material is obtained by fixing the orientation state. Others
Recently, many studies have been made on the use of a high-degree orientation of a liquid crystalline polymer thin film to form an orientation film of a low-molecular nematic liquid crystal.

In the present invention, the liquid crystalline polymer having a photoactive group is not intended to obtain a high-strength material, and a high degree of orientation of the polymer thin film is formed thereon. This utilizes the fact that the orientation of the hydrophilic molecular layer can be sufficiently controlled.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The liquid crystalline polymer having a photoactive group used in the present invention is a liquid crystalline polymer that causes a change in the molecular axis alignment of the photoactive group upon irradiation with linearly polarized light. The change in the molecular axis orientation as referred to herein means a phenomenon in which the direction of the molecular axis changes to a certain direction according to the linearly polarized light after absorbing the light energy of the linearly polarized light.

All of the groups having the property of causing a change in the molecular axis orientation of the photoactive group upon irradiation with linearly polarized light are included in the photoactive group in the present invention. Examples of such a photoactive group include a group containing at least one double bond selected from N = N, C = C, and C = N, wherein the double bond is non-aromatic. .

As a group having a non-aromatic N = N bond
Represents an azobenzene group, an azonaphthalene group, a bisazo group,
Aromatic azo groups such as formazan groups, and azoxybenze
And the like. Preferred of these groups
For example, the following formula: -N = N-AX-OCO (CH2)_P Op-phe-N = NB-
Y-AN = N-p-phe-Y (wherein A and B are benzene rings which may have a substituent)
Or a naphthalene ring, and X is (C₁~ C₁₀) Alkoki
Si group or di (C₁~ C₃) Represents an alkylamino group,
The alkyl groups in the alkylamino group may be the same,
And may be unsubstituted or one or both
It may be substituted with an ano group or a hydroxy group.
Y represents a hydrogen atom, a fluorine atom, a chlorine atom, a nitro group,
No group, (C ₁~ C₁₀) Alkyl group, (C₁~ C₁₀)
An alkoxy group, (C₁~ C₄) Alkyloxycarboni
Ruvinyl group, di (C1-C3) alkylamino group, dihi
Droxyethylamino group, hydroxy (C1-C3)
Alkylamino group, dicyanoethylamino group or cyanoe
Represents a tyl (C1-C3) alkylamino group, respectively.
P represents an integer of 1 to 10, and phe represents a benzene ring.
And p-phe or o-phe represents two substituents
Position or ortho position. )
I can do it.

Examples of the group having a non-aromatic C ＝ C bond include groups of polyene, stilbene, stilbazole, stilbazolium, cinnamic acid, indigo, thioindigo, hemithioindigo and the like. Preferred examples of these groups include, for example, the following formula: —CH ＝ C (X ₁ ) (X ₂ ) (wherein one of X _{1 and} X ₂ represents a hydrogen atom, and the other represents an aromatic 6 which may have a substituent. A membered ring, a (C ₁ -C ₃ ) alkoxycarbonyl group, or a group represented by —S-o-phe-CO— in which X 1 and X 2 are bonded.
o-phe may have a substituent. The substituents on the aromatic 6-membered ring and the phe group include those described for Y above. ).

As a group having a non-aromatic C = N bond
Include aromatic Schiff bases, aromatic hydrazone groups, etc.
The following formula -NH-N = C (X₃) (X₄) -N = CH-BY-A-CH = N-p-phe-Y (wherein X₃And X₄Is a hydrogen atom or lower alkoxy
Represents a cyclocarbonyl group, the other being a group represented by -BY
Represents a lower alkoxycarbonyl group, or X ₃as well as
X₄Are bonded to form -CH = NN (lower alkyl
I) represents a group represented by -CO-. A, B, Y,
p-phe and the like have the same meaning as described above. Group represented by)
And the like.

The wavelength of light absorbed by these liquid crystalline polymer compounds having a photoactive group is not limited to that in the visible light range but also includes those in the ultraviolet and infrared regions. When a thin film of the liquid crystalline polymer compound having a photoactive group is irradiated with linearly polarized light including a wavelength range that the compound absorbs, a change in molecular axis alignment easily occurs.

As the liquid crystalline polymer having a photoactive group used in the present invention, for example, a liquid crystalline polycondensation polymer such as polyamide, polyimide and polyester having a photoactive group, or a photoactive group is bound. Examples thereof include liquid crystalline polyaddition reaction polymers such as polyurethane and liquid crystalline polyvinyl cinnamate. The liquid crystalline polymer is a homopolymer obtained by reacting a monomer having a photoactive group, and reacting a monomer having a photoactive group with a monomer having no photoactive group, preferably a monomer of the same kind. Any of the copolymers may be used. In the case of the copolymer, a polymer obtained by polymerizing a monomer having no photoactive group, preferably a monomer of the same kind, in a proportion of 100 mol or less with respect to 1 mol of a monomer having a photoactive group is more preferable. Preferably the same monomer 5 having no photoactive group
Polymers polymerized in a proportion of 0 mol or less are preferred.

Specific examples of the liquid crystalline polymer include a partial structure represented by the following general formulas (1) to (4), and the entire polymer is substantially constituted by this partial structure. The homopolymer, the homopolymer of liquid crystalline polyvinyl cinnamate, or the partial structure or the partial structure corresponding to vinyl cinnamate is a mole ratio of about 1% or more, more preferably 2% or more.
% Or more.

The following general formula (1)

[0023]

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Wherein R represents a methyl group, an ethyl group, an i-propyl group or a chlorine atom, and n represents an integer of 5 to 10000. Z represents a group represented by the following formulas (a) to (e). Represent.

(A) -N = N-A-X (b) -CH = C (X ₁ ) (X ₂ ) (c) -NH-N = C (X ₃ ) (X ₄ ) (d)- N = CH-B-Y ( e) -OCO (CH 2) P O-p-phe-N = N
-BY

(In the above formula, A may have a substituent.
X represents (C) a benzene ring or a naphthalene ring;₁~ C₁₀)
An alkoxy group or di (C₁~ C₃) Alkylamino group
Represents an alkyl group in the dialkylamino group
Same or different, unsubstituted or one sided
Are both substituted with a cyano group or a hydroxy group
You may. One of X1 and X2 represents a hydrogen atom,
An aromatic six-membered ring, the other of which may have a substituent, (C₁~ C
₃) Represents an alkoxycarbonyl group or X1 and
A group represented by -S-o-phe-CO-, to which X2 is bonded;
Is shown. Also, X ₃And X₄Is hydrogen or lower
Represents an alkoxycarbonyl group, and the other is represented by -BY
Represents a lower group or a lower alkoxycarbonyl group, or
X₃And X ₄Are bonded to form -CH = NN (lower
Alkyl) -CO-. Also, B is
Benzene ring or naphthalene ring which may have a substituent
And Y is a hydrogen atom, a fluorine atom, a chlorine atom, a nitro group,
Cyano group, (C₁~ C₁₀) Alkyl group, (C₁~ C
₁₀) Alkoxy group, (C₁~ C₄) Alkyloxyca
Rubonyl vinyl group, di (C1-C3) alkylamino
Group, dihydroxyethylamino group, hydroxy (C1-
C3) an alkylamino group, a dicyanoethylamino group or
Each cyanoethyl (C1-C3) alkylamino group
Represent. P represents an integer of 1 to 10;
Represents a zen ring, and p-phe or o-phe is two-substituted
Indicates that the group is in the para or ortho position. )
A polyamide compound having a partial structure.

The following general formula (2)

[0028]

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Wherein R 1 is a residue of an alicyclic or aromatic tetracarboxylic acid, n ′ is an integer of 2 to 10,000,
₂ represents a group having a photoactive group represented by the following formula (f) or (g).

Equation (f)

[0031]

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(Wherein Z ₁ is Yp-phe-N = N-B _0- , Y-p-phe-N = CH-B ₀ -or Yp-phe-CH = N-B _0- Wherein B ₀ represents B or —C ₆ H ₄ O (CH
₂₎ shows the _P CO-, Y in the formula, p-phe, B and p
Have the same meanings as described above. Q represents an integer of 2 to 4. ) Or the following formula (g)

[0033]

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(Wherein Z ₁ has the same meaning as described above, r is an integer of 1 to 5, and s is an integer of 2 to 8), or a polyimide compound having a partial structure represented by the following general formula: Equation (3)

[0035]

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(Wherein R ₂ has the same meaning as in the above formula (2), R ₃ represents-(CH 2) m-, m represents 2 to 8, and n represents 5 to 10,000) A polyurethane compound having a partial structure represented by:
The following general formula (4)

[0037]

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[0038] (wherein _{Z 2} is (a) -N = N-A -X or _{(e) -OCO (CH2) P} O-p-phe-N = N
Represents a group represented by -BY, wherein A, X, p, p-
Each symbol of phe, B and Y has the same meaning as in the general formula (1). R ₄ represents a benzene ring, a naphthatan ring, C 4
Represents a 4-C6 methylene group (such as a tetramethylene group and a hexamethylene group), and n represents an integer of 5 to 10,000. A) a polyester compound having a partial structure represented by

Preferred examples of the above include the following. (1) Z is said in the general formula (1) (a) -N = N-A-X or the _{(e) -OCO (CH2) P} O-p-phe-N
= A polyamide compound having a partial structure of NBY. (2) In the general formulas (2) and (3), a polyimide compound or polyurethane having a partial structure in which Z ₁ in the formula (f) or (g) is Yp-phe-N = NA-. Compound. (3) A polyester compound having a partial structure represented by the general formula (4). (4) Homopolymer or copolymer of liquid crystalline polyvinyl cinnamate.

Among these, the liquid crystalline polycondensation polymer and the liquid crystalline polyaddition polymer of the above (1) to (3) are prepared by preparing a bifunctional monomer having a photoactive group and preparing the other bifunctional monomer. The desired liquid crystalline polymer compound (homopolymer) can be obtained by reacting the monomer with an equimolar amount. When producing a copolymer, a bifunctional monomer having a photoactive group is used together with, for example, the same type of bifunctional monomer having no photoactive group, and is equimolar to the other difunctional monomer in the same manner as described above. And a liquid crystalline polymer compound comprising a desired copolymer can be obtained. The amount of the photoactive group in the polymer compound can be adjusted by changing the usage ratio of the monomer having the photoactive group and the same type of monomer having no photoactive group. As the other bifunctional monomer to be reacted with the bifunctional monomer having a photoactive group, for example, 4,4 ′
-Diamino-3,5,3 ', 5'-tetra R-substituted-diphenylmethane (R has the same meaning as in the above formula (1)), alicyclic or aromatic tetracarboxylic acid, having 2 to 2 carbon atoms And 8 aliphatic dicarboxylic acids. Examples of the alicyclic or aromatic tetracarboxylic acid include an alicyclic or aromatic tetracarboxylic acid having 4 to 6 membered carbon atoms, and a fused ring tetracarboxylic acid having 4 carboxyl groups on a fused ring having 8 to 10 carbon atoms. Or a condensed ring having two carboxyl groups on a 4- to 6-membered alicyclic or aromatic ring having two carboxyl groups or an aromatic ring or a condensed ring having 8 to 10 carbon atoms via a bridging group or not And a two-bonded tetracarboxylic acid. The crosslinking group is not particularly limited, but includes a lower alkylene group, CO, a nitrogen atom, an oxygen atom and the like.

The homopolymer of liquid crystalline polyvinyl cinnamate can be obtained by polymerizing a vinyl cinnamate monomer. When a copolymer is obtained, it is possible to obtain a liquid crystalline polymer compound composed of a desired copolymer by polymerizing with a monomer capable of forming an appropriate copolymer and not inhibiting liquid crystallinity and having no photoactive group. I can do it. By changing the ratio of the vinyl cinnamate monomer to the monomer having no photoactive group, the amount of the photoactive group in the polymer compound can be adjusted. Monomers having no photoactive group to be copolymerized with a vinyl cinnamate monomer to obtain a copolymer include, for example, 4- (4′-n-pentyl) phenylstyrene and 4- (4′-n-hexyl) phenyl Styrene, 4- (4'-n-pentyl) cyclohexylstyrene, 4- (4'-n-hexyl) cyclohexylstyrene, and the like are included.

The proportion of the bifunctional monomer having a photoactive group and the monomer having no photoactive group to be reacted with the bifunctional monomer having a photoactive group to obtain a copolymer is a single ratio. Although it depends on the structure of the body, it is in the range of 1: 0 to 1: 100, more preferably 1: 0 to 1:50.

The polymerization reaction is carried out by a conventionally known polyamide compound,
It may be carried out by a solution polymerization method or the like usually in a solvent according to a conventionally known method for obtaining a polyimide compound, a polyurethane compound or a polyester compound, and a polyvinyl cinnamate polymer.

The degree of polymerization of the liquid crystalline polymer having a photoactive group used in the present invention obtained as described above is not particularly limited, and differs depending on the type of the resin, the type of the photoactive group and the like. Although it cannot be said, it is usually 2 or more, preferably 5 or more, more preferably 10 or more and 10,000 or more.
It is about.

The bifunctional monomer having a photoactive group includes
For example, ortho-phthalate having photoactive group on benzene nucleus
An acid, a nitrogen atom substituted by two alkyl groups,
Di [amino (C₂-C₄A)
Alkyl or amino (C₂-C ₈) Alkylaminocar
Bonil (C₁-C₅) Alkyl] amines and the like
You.

Specific examples of the bifunctional monomer having a photoactive group as a raw material of the liquid crystalline polymer used in the present invention are shown below, but these are merely examples, and the present invention is not limited to these. Absent.

(1) Non-aromatic N = N as a photoactive group
Examples of the monomer having a group having a bond include the following. Suitable monomers for polyamide or polyester compounds

[0048]

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[0049]

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[0050]

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Suitable monomers for polyimide or polyurethane compounds

[0052]

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[0053]

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(2) Non-aromatic C = N as photoactive group
Examples of the monomer having a group having a bond include the following. Suitable monomers for polyamide or polyester compounds

[0055]

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Suitable monomers for polyamide or polyester compounds

[0057]

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(2) Non-aromatic C ＝ C as photoactive group
Examples of the monomer having a group having a bond include the following. Suitable monomers for polyamide or polyester compounds

[0059]

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Suitable monomers for polyimide compounds or polyurethane compounds

[0061]

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As a method of providing such a thin film of a liquid crystalline polymer compound having a photoactive group on a substrate, a spin coating method is preferable. Further, this kind of liquid crystalline polymer thin film may be provided on a substrate by a Langmuir-Blodgett method. Further, the substrate may be immersed in these liquid crystalline polymer solutions and absorbed. The film thickness is usually preferably about 5 μm or less, more preferably 3 μm or less, and 1 μm or less is sufficient. When these coating films are provided, the liquid crystalline polymer is usually dissolved in an appropriate solvent and used as a liquid crystalline polymer solution. The concentration of the liquid crystalline polymer in the solution cannot be unconditionally determined because the appropriate concentration varies depending on the type of the liquid crystalline polymer, the degree of polymerization, the coating method, the desired film thickness, and the like. About 10 to 10% by weight, preferably 0.1 to 10% by weight.
It is about 5% by weight to 5% by weight. Suitable concentrations can be readily determined by preliminary testing of the application method used. The solvent used is not particularly limited as long as it dissolves the liquid crystalline polymer, but is usually pyridine, dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidinone (NMP),
Aprotic polar solvents such as dimethylacetamide (DMAC) and dimethylimidazoline (DMI) are preferred.

As a method of irradiating a thin film of a liquid crystalline polymer compound having a photoactive group provided on a substrate with linearly polarized light, various known methods can be applied. In order to manufacture a micro-pattern polarizing element, it is necessary to print a polarizing pattern on a liquid crystalline polymer thin film having a photoactive group,
For this purpose, the thin film may be irradiated with linearly polarized light through a desired mask pattern. Alternatively, a laser beam having a polarizing property may be condensed using a lens or the like, and the laser beam may be manipulated and irradiated in a pattern. Exposure energy is 1mJ / c
The range is preferably from m2 to 10 J / cm2. The change in molecular axis orientation due to the irradiation of linearly polarized light on the thin film is reversible, and the pattern can be freely overwritten by irradiating linearly polarized light with a different polarization axis for each mask pattern. still,
If one polarizing element (plate) having a complicated pattern is manufactured, the polarizing element (plate) having a complicated pattern is irradiated with linearly polarized light by using the polarizing element (plate) as a mask pattern. A large number can be manufactured by such a simple method.

The dichroic dye molecules are merely adsorbed in a micropattern on the thus obtained liquid crystalline polymer thin film having a photoactive group having a molecular axis arranged in a certain direction, that is, the dichroic dye molecules are deposited on the thin film. Just by providing the color dye layer in a micro pattern, the molecular axes of the dichroic dye molecules are arranged in the direction of the molecular axis of the photoactive group, that is, in the direction defined by the polarization axis of the linearly polarized light applied to the thin film. In addition, the polarization axis is fixed, and the properties as a micro-pattern polarizing element are exhibited. In the case of the micropattern polarizing element obtained in this way, the dichroic ratio (DR) at the absorption maximum wavelength can be 10 or more, preferably 20 or more, and more preferably 30 or more. . To explain this more specifically, a dichroic dye solution is applied to a substrate having a liquid crystalline polymer thin film having a photoactive group in which molecular axes are arranged in a certain direction, and a desired temperature and humidity condition is applied. The solvent is evaporated underneath to form the dye thin film in a micro pattern.
At this time, the molecular axis of the dye is arranged in the direction defined by the polarization axis of the linearly polarized light irradiated on the liquid crystalline polymer thin film having a photoactive group, and the light absorption axis of the dye thin film is fixed, so that the micro-patterned polarization The properties as an element are exhibited. Solvents for dissolving dichroic dyes include water, alcohols, ethers, pyridine, dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidinone (NMP), dimethylacetamide (DMAC)
Aprotic polar solvents such as dimethylimidazoline (DMI) are preferred. Particularly, a mixed solvent mainly composed of water is preferable. The mixing amount of the organic solvent is arbitrary, but is preferably 0 to 70%, particularly preferably 0 to 50%. Also, a small amount of a surfactant can be added.

The temperature and humidity conditions under which the solvent of the dichroic dye solution is evaporated to form the dye thin film are important conditions that affect the performance of the dye thin film as a polarizing element. The conditions are determined by the solvent composition, the type of dye, the dye concentration, the coating film thickness, etc., and the temperature is 0 to 200 ° C., preferably 5 to 200 ° C.
50 ° C, humidity 20-80% RH, preferably 40-7
It is about 0% RH.

The dichroic dye used in the present invention is a compound exhibiting lyotropic liquid crystallinity under a certain solvent composition, dye concentration and temperature conditions, and forms an associated aggregate called a chromonic liquid crystal phase. When the aggregates are arranged in a certain direction, they exhibit polarizability. Further, it has a feature of being excellent in light fastness because a plurality of molecules are associated. For example, a compound having an aromatic ring structure is preferable. As the aromatic ring structure, benzene, naphthalene, anthracene, phenanthrene besides thiazole,
Heterocycles such as pyridine, pyrimidine, pyridazine, pyrazine and quinoline or quaternary salts thereof, and condensed rings thereof with benzene, naphthalene, etc. are particularly preferred. or,
It is preferable that a hydrophilic substituent such as a sulfonic acid group, a carboxylic acid group, an amino group, or a hydroxyl group is introduced into these aromatic rings.

The dichroic dyes include, for example, azo dyes,
Cyanine dyes, anthraquinone dyes including condensed dyes such as indanthrone, stilbene dyes, pyrazolone dyes, perylene dyes, naphthalimide dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes Dyes, quinophthalone dyes, indigo dyes, thioindigo dyes and the like can be mentioned. Water-soluble dyes are preferred, but not limited thereto. Specific examples of dichroic dyes include, for example, CIDirect Blue 1, CIDirect Blue
15, CIDirect Blue 67, CIDirect Blue 78, C.
I.Direct Blue 83, CIDirect Blue 90, CIDirect Blu
e 98, CIDirect Blue 151, CIDirectBlue 168, C.
I.Direct Blue 202, CIDirect Green 51, CIDirect
Green 59, CIDirect Green 85, CIDirect Vioet 9,
CIDirect Vioet 48, CIDirectRed 2, CIDirect R
ed 39, CIDirect Red 79, CIDirect Red 81, CID
irect Red 83, CIDirect Red 89, CIDirect Orange
39, CIDirect Orange 41, CIDirect Orange 49,
CIDirect Orange 72, CIDirect Yellow 12, CIDi
rect Yellow 26, CIDirect Yellow 44, CIDirect Y
ellow 50, CIAcidRed 37, CINo.27865, CINo.27
915, CINo.27920, CINo.29058, CINo.29060, dis
ufoindanthrone, disulfo-N, N'-dixylylperylenetetrac
arbodiimide and the like. Next, some specific examples are shown by structural formulas below.

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EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, parts are by weight unless otherwise specified.

Example 1 Synthesis of polyamide compound (1) In 50 parts of NMP, 3.7 parts of 5- (4'-n-hexyloxyphenylazo) isophthalic acid and 4,4'-diamino-3,5,3 ', 5'-tetraethyldiphenylmethane (TEDPM: Nippon Kayaku 3.1 parts) and dissolve with stirring. Then triphenylphosphite 9.3
And 2.4 parts of pyridine, and the mixture is stirred and reacted at 100 ° C. for 10 hours. After the completion of the reaction, 30 parts of water is added, the supernatant is removed by decantation, and 100 parts of a 2% aqueous sodium carbonate solution is added, followed by stirring overnight to crystallize. The generated crystals are filtered, washed with water and dried to obtain 6.4 parts of the polyamide compound (1). Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Preparation of photoactive group-containing polyamide thin film and irradiation of linearly polarized light. 2 parts of the purified polyamide compound (1) is dissolved in 98 parts of NMP to prepare a 2% polymer solution. Next, the polyamide thin film is formed by spin coating on a glass substrate so as to have a dry film thickness of about 0.6 to 0.7 μm and drying by heating at 180 ° C. for 10 minutes. Using an ultra-high pressure mercury lamp (500 W / hr) to make visible light with a 400 nm cut-off filter,
Further, after linearly polarized light is passed through a polarizing plate, the film surface of the glass substrate on which the polyamide thin film is formed is irradiated through a stripe-shaped mask for 1 minute from a distance of 50 cm from the surface of the glass substrate. They are arranged in a certain direction.

Preparation of associative dichroic dye film. A dye solution is prepared by dissolving 1 part of CIDirect Blue 67 and 0.02 part of Emulgen 108 (Nonionic surfactant: manufactured by Kao Corporation) in 8.98 parts of deionized water. This dye solution is spin-coated on the film surface of the polyamide thin film substrate, and dried under the conditions of 40 ° C. and 60% RH to obtain the stripe-shaped polarizing element of the present invention. FIG. 1 shows the visible absorption spectrum. The dichroic ratio at the absorption maximum wavelength is 25
Met.

Synthesis of 5- (4′-n-hexyloxyphenylazo) isophthalic acid used as a starting material for polyamide compound (1). To 70 parts of water are added 21.9 parts of diethyl 5-aminoisophthalate and 31 parts of 6N hydrochloric acid, and the mixture is cooled with ice water.
6.4 parts of sodium nitrite are dissolved in 20 parts of water, and added at 5 ° C. or lower to diazotize. Separately, a coupling solution of 8.7 parts of phenol, 11.2 parts of sodium carbonate and 100 parts of water is prepared and cooled with ice water. 5 ° C in this coupling solution
The above diazonium solution is added below, and the mixture is stirred at 10 ° C. or less overnight. Next, 20 parts of 6N hydrochloric acid was added, followed by filtration, washing with water and drying to obtain 28.7 parts of monoazo dye 5- (4'-oxyphenylazo) isophthalic acid diethyl ester. Next, the above monoazo dye 11.6 was added to 60 parts of DMF.
Part, 3.6 parts of sodium carbonate, n-hexyl bromide
4 parts are charged and stirred and reacted at 100 ° C. for 10 hours. After the reaction, 120 parts of water is added and the mixture is stirred overnight. The precipitated crystals are filtered and washed with water. Furthermore, this wet cake is
In a solution of 4.1 parts of caustic soda in 5 parts
The mixture is stirred and reacted at 5-65 ° C for 4 hours. After the end of the reaction, water 200
Then, 6N hydrochloric acid was added for neutralization, and the precipitated crystals were filtered, washed with water, and dried to give 5- (4'-).
4. n-hexyloxyphenylazo) isophthalic acid
Get 6 parts.

Example 2 Synthesis of polyamide compound (2) 5- (4'-methoxyphenylazo) in 50 parts of NMP
3.0 parts of isophthalic acid, 4,4′-diamino-3,
5,3 ', 5'-tetraethyldiphenylmethane (TE
DPM) and dissolve with stirring. Next, 9.3 parts of triphenylphosphite and 2.4 parts of pyridine are added, and the mixture is stirred and reacted at 100 ° C. for 10 hours. After the completion of the reaction, 30 parts of water was added, and the supernatant was removed by decantation and 2%
100 parts of a sodium carbonate aqueous solution is added, and the mixture is stirred overnight to be crystallized. The generated crystals are filtered, washed with water and dried to obtain 5.7 parts of a polyamide compound (2). Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Preparation of photoactive group-containing polyamide thin film and irradiation of linearly polarized light. 2 parts of the above purified polyamide compound (2) is dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 1, and linearly polarized light was irradiated for 1 minute from a distance of 50 cm onto the film surface of the glass substrate on which the polyamide thin film was formed via a stripe-shaped mask. The molecular axes of the photoactive groups are arranged in a certain direction.

Preparation of associative dichroic dye film. One part of Benzopurpurine 4B and 0.02 part of Emulgen 108 (trade name: Nonionic surfactant: manufactured by Kao Corporation) are dissolved in 8.98 parts of deionized water by heating to prepare a dye solution. This dye solution is spin-coated on the film surface of the polyamide thin film substrate, and dried under the conditions of 40 ° C. and 60% RH to obtain the stripe-shaped polarizing element of the present invention. FIG. 2 shows the visible absorption spectrum. The dichroic ratio at the maximum absorption wavelength was 30.

Synthesis of 5- (4′-methoxyphenylazo) isophthalic acid used as a starting material for polyamide compound (2). The monoazo dye 5- obtained in Example 1 was added to 100 parts of DMF.
17.1 parts of (4'-oxyphenylazo) isophthalic acid diethyl ester, 5.3 parts of sodium carbonate, and 18.6 parts of methyl toluenesulfonate are charged and stirred at 100 ° C. for 10 hours. After the reaction, 200 parts of water is added and the mixture is stirred overnight. The precipitated crystals are filtered and washed with water. Further, this wet cake is charged into a solution of 6.0 parts of caustic soda in 100 parts of methanol, and the mixture is stirred and reacted at 55-65 ° C. for 5 hours. After the completion of the reaction, 200 parts of water was added to confirm complete dissolution, and 6N hydrochloric acid was added to neutralize the mixture. The precipitated crystals were filtered, washed with water and dried, and 12.7 of 5- (4′-methoxyphenylazo) isophthalic acid was obtained. Get the part.

Example 3 Synthesis of polyamide compound (3) 3.1 parts of 5- (4′-dimethylaminophenylazo) isophthalic acid, 50 parts of NMP, 4,4′-diamino-
3.1 parts of 3,5,3 ', 5'-tetraethyldiphenylmethane (TEDPM: manufactured by Nippon Kayaku Co., Ltd.) is added and dissolved by stirring. Then triphenylphosphite 9.3
And 2.4 parts of pyridine, and the mixture is stirred and reacted at 100 ° C. for 10 hours. After completion of the reaction, 50 parts of water was added, the supernatant was removed by decantation, and 100 parts of a 2% aqueous sodium carbonate solution was added, followed by stirring overnight to crystallize. The generated crystals are filtered, washed with water and dried to obtain 5.9 parts of a polyamide compound (3). Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Preparation of photoactive group-containing polyamide thin film and irradiation of linearly polarized light. 2 parts of the above purified polyamide compound (3) is dissolved in 98 parts of NMP to prepare a 2% polymer solution. Next, the polyamide thin film is formed by spin coating on a glass substrate so as to have a dry film thickness of about 0.6 to 0.7 μm and drying by heating at 180 ° C. for 10 minutes. Using an ultra-high pressure mercury lamp (500 W / hr) to make visible light with a 500 nm cut-off filter,
Further, after linearly polarized light is passed through a polarizing plate, the film surface of the glass substrate on which the polyamide thin film is formed is irradiated through a stripe-shaped mask for 1 minute from a distance of 50 cm from the surface of the glass substrate. They are arranged in a certain direction.

Preparation of associative dichroic dye film. A dye solution is prepared by heating and dissolving 1 part of CIDirect Blue 67 and 0.02 part of Emulgen 108 (trade name: nonionic surfactant: manufactured by Kao Corporation) in 8.98 parts of deionized water. This dye solution is spin-coated on the film surface of the polyamide thin film substrate, and dried under the conditions of 40 ° C. and 60% RH to obtain the stripe-shaped polarizing element of the present invention. FIG. 3 shows the visible absorption spectrum. The dichroic ratio at the maximum absorption wavelength was 25.

Synthesis of 5- (4′-dimethylaminophenylazo) isophthalic acid used as a starting material for polyamide compound (3). 9.05 of 5-aminoisophthalic acid in 100 parts of ice water
And 17 parts of 6N hydrochloric acid, and the mixture is cooled with ice water. 3.45 parts of sodium nitrite are dissolved in 10 parts of water, and added at 5 ° C. or lower to diazotize. Separately, N, N-dimethylaniline 6.3
, 8.5 parts of 6N hydrochloric acid and 60 parts of ice water are prepared and cooled with ice water. 5 in this coupling solution
The above diazonium solution is added at a temperature of not more than 0 ° C., and the mixture is stirred overnight at a temperature of not more than 10 ° C. while maintaining pH 4 to 6 by adding a 2% sodium carbonate solution. The precipitated crystals are filtered, washed with water and dried to obtain 15.5 parts of monoazo dye 5- (4'-dimethylaminophenylazo) isophthalic acid.

Example 4 Synthesis of polyamide compound (4). In 50 parts of NMP, 5.9 parts of 5- (4 ′-(4 ″ -dimethylaminophenylazo) phenoxyundecanoyloxy) isophthalic acid and 4,4′-diamino-3,5,
3 ', 5'-tetraethyldiphenylmethane (TEDP
M) Add 3.1 parts and stir to dissolve. Next, 9.3 parts of triphenylphosphite and 2.4 parts of pyridine were added, and 1
Stir at 00 ° C for 10 hours. After the completion of the reaction, 30 parts of water is added, the supernatant is removed by decantation, and 100 parts of a 2% aqueous sodium carbonate solution is added, followed by stirring overnight to crystallize.
The generated crystals are filtered, washed with water and dried to obtain 8.7 parts of a polyamide compound (4). Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Preparation of photoactive group-containing polyamide thin film and irradiation with linearly polarized light. 2 parts of the above purified polyamide compound (4) is dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed in the same manner as in Example 3, and linearly polarized light was irradiated from a distance of 50 cm to the film surface of the glass substrate on which the polyamide thin film was formed for 1 minute through a stripe-shaped mask. The molecular axes of the photoactive groups are arranged in a certain direction.

Preparation of associative dichroic dye film. One part of CIDirect Blue 1 and 0.02 part of Emulgen 108 (Nonionic surfactant: manufactured by Kao Corporation) are dissolved in 8.98 parts of deionized water by heating to prepare a dye solution. This dye solution is roll-coated on the film surface of the above-mentioned polyamide thin film substrate, and dried under the conditions of 30 ° C. and 60% RH to obtain the striped polarizing element of the present invention. The dichroic ratio at the maximum absorption wavelength was 30.

Synthesis of 5- (4 ′-(4 ″ -dimethylaminophenylazo) phenoxyundecanoyloxy) isophthalic acid used as a raw material of polyamide compound (4) 4-oxy (4′-dimethylaminophenylazo) ) 4- synthesized from benzene and 11-bromoundecanoic acid
8.5 parts of (4′-dimethylaminophenylazo) phenoxyundecanoic acid and 9.6 parts of thionyl chloride are dissolved in toluene 3
The reaction is stirred for 5 hours at room temperature in 0 parts. Thereafter, excess thionyl chloride was distilled off under reduced pressure, and the mixture was cooled with ice water to give 5-
Ditetrapyranyl oxyisophthalate 7.5
And 9.6 parts of pyridine are dissolved in 20 parts of DMF. The mixture is stirred and reacted at 5-10 ° C for 15 hours. After the completion of the reaction, the mixture was diluted with 500 parts of a 2% aqueous sodium carbonate solution, and toluene
Add 0 parts and separate. The toluene layer is washed with water, dried over anhydrous sodium sulfate, and toluene is distilled off under reduced pressure to obtain an oil. This is dissolved in 100 parts of dioxane, 10 parts of concentrated hydrochloric acid is added, and the mixture is stirred and reacted to hydrolyze the ester group. Neutralized with a 5% aqueous sodium carbonate solution, the precipitated crystals were filtered, washed with water and dried.
A crude product of (4 ′-(4 ″ -dimethylaminophenylazo) phenoxyundecanoyloxy) isophthalic acid is obtained, and recrystallized with alcohol to obtain a purified product.

The polyamide compounds shown in Table 1 were obtained in the same manner as in Example 4, and the same photo-alignment effect was obtained.

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Example 5 A method for separately synthesizing the polyamide compound (4). 8.5 parts of 4- (4′-dimethylaminophenylazo) phenoxyundecanoic acid and 9.6 parts of thionyl chloride are stirred and reacted in 30 parts of toluene at room temperature for 5 hours. Thereafter, excess thionyl chloride was distilled off under reduced pressure, and poly (imino-5-oxyisophthaloylimino-1,1) was added while cooling with ice water.
4- (3,5-diethyl) phenylene-methylene-1,
A solution prepared by dissolving 4.6 parts of 4- (3,5-diethyl) phenylene and 9.6 parts of pyridine in 100 parts of NMP is added dropwise.
The mixture is stirred and reacted at 5-10 ° C for 15 hours. 2% after reaction
After diluting with 500 parts of an aqueous sodium carbonate solution and distilling off toluene, the precipitated crystals are filtered, washed with water and dried. The crude polyamide is dissolved in a small amount of NMP by heating, diluted with methanol, and purified by reprecipitation. From the NMR measurement, it was clear that about 50% of the oxy groups were substituted with 4- (4'-dimethylaminophenylazo) phenoxyundecanoyl groups.

Example 6 Synthesis of polyamide compound (6). In 50 parts of NMP, 3.6 parts of 5- (4′-dimethylaminonaphthylazo) isophthalic acid, 4,4′-diamino-
3.1 parts of 3,5,3 ', 5'-tetraethyldiphenylmethane (TEDPM: manufactured by Nippon Kayaku Co., Ltd.) is added and dissolved by stirring. Then triphenylphosphite 9.3
And 2.4 parts of pyridine, and the mixture is stirred and reacted at 100 ° C. for 10 hours. After completion of the reaction, 50 parts of water was added, the supernatant was removed by decantation, and 100 parts of a 2% aqueous sodium carbonate solution was added, followed by stirring overnight to crystallize. The generated crystals are filtered, washed with water and dried to obtain 6.4 parts of a polyamide compound (6). Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Preparation of photoactive group-containing polyamide thin film and irradiation of linearly polarized light. 2 parts of the above purified polyamide compound (6) is dissolved in 98 parts of NMP to prepare a 2% polymer solution. Next, the polyamide thin film is formed by spin coating on a glass substrate so as to have a dry film thickness of about 0.6 to 0.7 μm and drying by heating at 180 ° C. for 10 minutes. Using an ultra-high pressure mercury lamp (500 W / hr) to make visible light with a 550 nm cut-off filter,
Further, after linearly polarized light is passed through a polarizing plate, the film surface of the glass substrate on which the polyamide thin film is formed is irradiated through a stripe-shaped mask for 1 minute from a distance of 50 cm from the surface of the glass substrate. They are arranged in a certain direction.

Preparation of associative dichroic dye film. A dye solution is prepared by heating and dissolving 1 part of CIDirect Blue 67 and 0.02 part of Emulgen 108 (trade name: nonionic surfactant: manufactured by Kao Corporation) in 8.98 parts of deionized water. This dye solution is spin-coated on the film surface of the polyamide thin film substrate, and dried under the conditions of 40 ° C. and 60% RH to obtain the stripe-shaped polarizing element of the present invention. FIG. 4 shows the visible absorption spectrum. The dichroic ratio at the maximum absorption wavelength was 25.

Synthesis of 5- (4'-dimethylaminonaphthylazo) isophthalic acid used as a raw material of polyamide compound (6). 9.05 of 5-aminoisophthalic acid in 100 parts of ice water
And 17 parts of 6N hydrochloric acid, and the mixture is cooled with ice water. 3.45 parts of sodium nitrite are dissolved in 10 parts of water, and added at 5 ° C. or lower to diazotize. Separately, a coupling solution of 8.9 parts of 1-N, N-dimethylnaphthylamine, 8.5 parts of 6N hydrochloric acid and 60 parts of ice water is prepared and cooled with ice water. The above diazonium solution is added to the coupling solution at 5 ° C. or less,
10% sodium carbonate solution while maintaining the pH 4-6.
Stir below ℃ overnight. The precipitated crystals are filtered, washed with water and dried to obtain 15.8 parts of monoazo dye 5- (4'-dimethylaminonaphthylazo) isophthalic acid.

Example 7 Synthesis of polyamide compound (7). 5- (4'-methoxynaphthylazo) in 50 parts of NMP
3.5 parts of isophthalic acid, 4,4′-diamino-3,
5,3 ', 5'-tetraethyldiphenylmethane (TE
DPM) and dissolve with stirring. Next, 9.3 parts of triphenylphosphite and 2.4 parts of pyridine are added, and the mixture is stirred and reacted at 100 ° C. for 10 hours. After the completion of the reaction, 50 parts of water was added, and the supernatant was removed by decantation and 2%
100 parts of a sodium carbonate aqueous solution is added, and the mixture is stirred overnight to be crystallized. The generated crystals are filtered, washed with water and dried to obtain 3.5 parts of a polyamide compound (7). Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Preparation of photoactive group-containing polyamide thin film and irradiation of linearly polarized light. 2 parts of the purified polyamide compound (7) is dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 1, and linearly polarized light was irradiated for 1 minute from a distance of 50 cm onto the film surface of the glass substrate on which the polyamide thin film was formed via a stripe-shaped mask. The molecular axes of the photoactive groups are arranged in a certain direction.

Preparation of associative dichroic dye film. One part of Benzopurpurine 4B and 0.02 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) are heated and dissolved in 8.98 parts of deionized water to prepare a dye solution. This dye solution is spin-coated on the film surface of the polyamide thin film substrate, and dried under the conditions of 40 ° C. and 60% RH to obtain the stripe-shaped polarizing element of the present invention. FIG. 5 shows the visible absorption spectrum. The dichroic ratio at the absorption maximum wavelength is 30
Met.

Synthesis of 5- (4'-methoxynaphthylazo) isophthalic acid used as a raw material of polyamide compound (7). 12.6 parts of 5-aminoisophthalic acid diethyl ester and 18 parts of 6N hydrochloric acid are added to 40 parts of water, and the mixture is cooled with ice water.
3.67 parts of sodium nitrite are dissolved in 10 parts of water, and added at 5 ° C. or lower to diazotize. Separately, 1-naphthol 7.7
Parts, 6.5 parts of sodium carbonate and 60 parts of water are prepared and cooled with ice water. 5 in this coupling solution
The above diazonium solution is added at a temperature of 10 ° C. or less, and the mixture is stirred at 10 ° C. or less overnight. Subsequently, 12 parts of 6N hydrochloric acid was added, followed by filtration, washing with water and drying to obtain 20.7 parts of monoazo dye 5- (4′-oxynaphthylazo) isophthalic acid diethyl ester. Next, the above monoazo dye 12.5 was added to 60 parts of DMF.
Parts, 2.9 parts of sodium carbonate, methyl toluenesulfonate 1
0.0 part is charged and stirred and reacted at 100 ° C. for 10 hours. After the reaction, 120 parts of water is added and the mixture is stirred overnight. The precipitated crystals are filtered and washed with water. Further, this wet cake is charged into a solution of 3.3 parts of caustic soda in 70 parts of methanol, and the mixture is stirred and reacted at 55-65 ° C. for 4 hours. Water 200 after reaction
Then, 6N hydrochloric acid was added for neutralization, and the precipitated crystals were filtered, washed with water, and dried to give 5- (4'-).
5.6 parts of methoxynaphthylazo) isophthalic acid are obtained.

Example 8 Synthesis of polyimide (8). 3.26 parts of 4-dimethylamino-4′-di (aminoethyl) aminophenylazobenzene and 60 parts of N-methyl-2-pyrrolidone are charged into a four-necked flask, and stirred and dissolved while blowing nitrogen under water cooling. Then cyclopentane-
2.1 parts of 1,2,3,4-tetracarboxylic anhydride are added little by little. After completion of the addition, 1 hour at 60 ° C under water cooling for 4 hours.
The reaction is performed for 0 hour to obtain a polyamic acid solution. N-
40 parts of methyl-2-pyrrolidone was added to prepare a 5% polyamic acid solution, and a dry film thickness of about 0.6 was formed on a glass substrate.
It is spin-coated so as to have a thickness of −0.7 μm and heated at 200 ° C. for 1 hour to obtain the polyimide thin film. Using a super-high pressure mercury lamp (500 W / hr), a 550 nm cut-off filter is used to make visible light, and then linearly polarized light is passed through a polarizing plate. After that, the polyamide thin film is formed on the surface of the glass substrate through a striped mask. Irradiation is performed for 1 minute from a distance of 50 cm to arrange the molecular axis of the photoactive group in the polarized light irradiation part in a fixed direction.

Preparation of associative dichroic dye film. One part of CIDirect Blue 67 and 0.02 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) are dissolved by heating in 8.98 parts of deionized water to prepare a dye solution. This dye solution is roll-coated on the film surface of the polyamide thin film substrate and dried under the conditions of 40 ° C. and 60% RH to obtain the stripe-shaped polarizing element of the present invention. The dichroic ratio at the maximum absorption wavelength was 25.

Example 9 Synthesis of polyimide (9). A four-necked flask was charged with 3.01 parts of N, N-diaminoethyl-4- (4 '-(4 "-dimethylaminophenylazo) phenoxyundecanoyloxy) aniline and 60 parts of N-methyl-2-pyrrolidone. The mixture is stirred and dissolved while blowing nitrogen under water cooling, and then 1.55 parts of 4,4'-oxydiphthalic anhydride is added little by little, and after completion of the addition, the mixture is reacted under water cooling for 4 hours and at 60 ° C. for 10 hours to obtain a polyamic acid solution. To which N-methyl-2-pyrrolidone 30 is added.
A 5% polyamic acid solution was prepared by adding a part, and spin-coated on a glass substrate to a dry film thickness of about 0.6 to 0.7 μm, and heated at 200 ° C. for 1 hour to obtain the polyimide thin film.

Example A polyimide shown in Table 2 can be obtained by reacting the following diamine and tetracarboxylic anhydride according to Examples 8 and 9.

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Example 10 The polyamide thin film coated substrate prepared in Example 1 was
Linearly polarized light obtained in the same manner as in Example 1 was irradiated onto the film surface of the glass substrate on which the polyamide thin film was formed for 1 minute from a distance of 50 cm through a stripe-shaped mask shown in FIG. The molecular axis of the photoactive group in the irradiated part is arranged in a certain direction. Next, the linearly polarized light rotated by 90 ° is irradiated for 1 minute from a distance of 50 cm onto the film surface of the unexposed portion of the substrate coated with the polyamide thin film through a stripe-shaped mask shown in FIG. The molecular axes of the photoactive groups in the portions are arranged in a direction different from 1 by 90 °.

Preparation of associative dichroic dye film. 1 copy of CIDirect Blue 1 and 1 copy of CIDirect Blue 67
Department, CIDirect Red 79 0.5 parts, CIDirect Orange
0.5 parts of 39 and 0.06 parts of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) in 26.94 of deionized water.
The mixture is heated and dissolved to prepare a dye solution. This dye solution is spin-coated on the film surface of the polyamide thin film substrate,
After drying under the conditions of 60 ° C. and 60% RH, two types of stripe-shaped polarizing elements of the present invention having different polarization axes by 90 ° are obtained.

Example 11 The polyamide thin film coated substrate prepared in Example 4 was
Linearly polarized light obtained in the same manner as in Example 4 was irradiated onto the surface of the glass substrate on which the polyamide thin film was formed for 1 minute from a distance of 50 cm through a stripe-shaped mask shown in FIG. The molecular axis of the photoactive group in the irradiated part is arranged in a certain direction. Next, the linearly polarized light rotated by 90 ° is irradiated for 1 minute from a distance of 50 cm onto the film surface of the unexposed portion of the substrate coated with the polyamide thin film through a stripe-shaped mask shown in FIG. The molecular axes of the photoactive groups in the portions are arranged in a direction different from 1 by 90 °.

Preparation of associative dichroic dye film. 1 copy of CIDirect Blue 83 and 1 copy of CIDirect Blue 67
Department, CIDirect Red 2 0.5 parts, CIDirect Orange
0.5 part of 39 and 0.06 part of Emulgen 108 (trade name: nonionic surfactant: manufactured by Kao Corporation) in deionized water 2
Heat and dissolve in 6.94 parts to prepare a dye solution. This dye solution is spin-coated on the surface of the above-mentioned polyamide thin film substrate and dried under the conditions of 40 ° C. and 60% RH. Get.

Example 12 The polyamide thin film coated substrate prepared in Example 1 was
Linearly polarized light obtained in the same manner as in Example 1 was irradiated on the surface of the glass substrate on which the polyamide thin film was formed for 1 minute from a distance of 50 cm, and the molecular axis of the photoactive group in the polarized light irradiation portion was arranged in a fixed direction. Let it.

Preparation of associative dichroic dye film. 3 parts of CIDirect Blue 15 and 0.02 part of Emulgen 108 (trade name: nonionic surfactant: manufactured by Kao Corporation) are dissolved in 6.98 parts of deionized water by heating to prepare a blue dye solution. Next, 3 copies of CIDirect Red 28, Emulgen 108
(Product name: Nonionic surfactant: manufactured by Kao Corporation) 0.0
2 parts are heated and dissolved in 6.98 parts of deionized water to prepare a red dye solution. Further, 3 parts of CIDirect Green 85 and Emulgen 108 (trade name: Nonionic surfactant: Kao Corporation)
(0.02 parts) was heated and dissolved in 6.98 parts of deionized water to prepare a green dye solution. This dye solution is printed on the surface of the above-mentioned polyamide thin film substrate separately in the form of stripes by screen printing in the form of blue, red and green, and dried under the conditions of 40 ° C. and 60% RH. To obtain a green stripe-shaped polarizing element.

[0118]

According to the present invention, a polarizing element can be obtained simply by arranging dichroic molecules in a micropattern on a liquid crystalline polymer thin film layer having a photoactive group irradiated with linearly polarized light. Since a stretching operation is not required, a polarizing element can be directly formed on a substrate that cannot be stretched such as a glass substrate. In addition, it is possible to change the arrangement of dichroic molecules only by changing the polarization axis of the linearly polarized light to be irradiated. Therefore, it has become possible to manufacture a micro-pattern polarization element having a different polarization axis on a substrate. A liquid crystal display device using this substrate can easily display a stereoscopic image.

[0119]

[Brief description of the drawings]

FIG. 1 is a visible absorption spectrum of a polarizing element obtained in Example 1 (in the figure, A (parallel) indicates the absorbance when the polarization axis is parallel to the molecular long axis of the alignment dye, and A (vertical) indicates the polarization axis) Indicates the absorbance when the vertical axis is perpendicular to the molecular long axis of the alignment dye.

FIG. 2 is a visible absorption spectrum of a polarizing element obtained in Example 2.

FIG. 3 is a visible absorption spectrum of a polarizing element obtained in Example 3.

FIG. 4 is a visible absorption spectrum of the polarizing element obtained in Example 4.

FIG. 5 is a visible absorption spectrum of the polarizing element obtained in Example 5.

FIG. 6 is a test mask in which light-shielding portions having a length of 50 mm and a width of a μm are arranged at intervals of b μm.

FIG. 7 is a test mask in which light-shielding portions having a length of 50 mm and a width of a μm are arranged at intervals of b μm. b> a,
When they are superimposed, the light-shielding portion of FIG. 7 is located between the light-shielding portions of FIG. 6.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Kunihiro Ichimura 2-23-16, Fujigaoka, Midori-ku, Yokohama-shi, Kanagawa Prefecture (72) Takashi Tamaki 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. In the laboratory

Claims (15)

[Claims] 1. A liquid crystal polymer thin film layer having a photoactive group on a substrate and a layer containing dichroic molecules in contact with the liquid crystal polymer thin film layer, wherein the dichroic molecules are arranged in a micro pattern. Polarizing element. 2. The photoactive group is a group containing at least one double bond selected from non-aromatic N ＝ N, non-aromatic C ＝ C, and non-aromatic C ＝ N. The polarizing element according to claim 1. 3. The polarizing element according to claim 1, wherein the liquid crystalline polymer thin film is a polyamide, polyimide, polyester, or polyurethane resin thin film. 4. The polarizing element according to claim 1, wherein the liquid crystalline polymer thin film is a polyvinyl cinnamate resin thin film. 5. The polarizing element according to claim 1, wherein the dichroic molecule is a dye having lyotropic liquid crystal properties. 6. The polarizing element according to claim 5, wherein the dye having lyotropic liquid crystallinity is a dye having a hydrophilic substituent. 7. The polarizing element according to claim 6, wherein the hydrophilic substituent is a sulfonic acid group, a carboxylic acid group, an amino group, or a hydroxyl group. 8. A liquid crystalline polymer thin film having a photoactive group is formed on a substrate, and the thin film is irradiated with linearly polarized light, and then dichroic molecules are arranged in a micro pattern on the thin film. A method for manufacturing a polarizing element. 9. The method for manufacturing a polarizing element according to claim 8, wherein the irradiation of the linearly polarized light is performed via a micropatterned mask. 10. The method according to claim 8, wherein the irradiation of the linearly polarized light is performed using a laser beam having a polarization property. 11. A liquid crystalline polymer thin film having a photoactive group is formed on a substrate, and the thin film is irradiated with linearly polarized light through a micro-patterned mask, and then irradiated through another micro-patterned mask. A method for producing a polarizing element, comprising irradiating linearly polarized light having different polarization axes and then arranging dichroic molecules on the thin film in a micropattern. 12. A three-dimensional display device, wherein at least one of the upper and lower substrates facing each other is a substrate having the polarizing element according to any one of claims 1 to 7. 13. A thin film of a liquid crystalline polymer having a photoactive group. 14. The photoactive group according to claim 13, wherein the molecular axes thereof are arranged in a micropattern in a certain direction.
Liquid crystalline polymer thin film described 15. The liquid crystalline polymer thin film according to claim 14, wherein the molecular axes of the photoactive groups are arranged in a lattice in a certain direction.