JP2002357720A - Method for manufacturing new micro pattern polarizing element and three dimensional liquid crystal display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To establish a method for manufacturing a micro pattern polarizing element having excellent partial orientation of a dichroic dye compound without necessitating extremely high positioning precision such as panel alignment. SOLUTION: The method for manufacturing the polarizing element consists of steps of: forming a liquid crystalline polymer thin film with an optically active group on a substrate; irradiating the thin film with linearly polarized light; then irradiating the thin film with linearly polarized light with a different axis of polarization via a different mask with a micro pattern; and aligning the dichroic molecules on the thin film in a micro pattern. The dichroic molecule solution is applied with a printing machine with low printing pressure such as a roll coater, a flexographic machine, a screen printing machine, etc., so as to apply 0.05 to 1.0 Mpa pressure in a direction vertical to the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel high-polarization micropattern polarizing element and its use. Further, the present invention relates to a micro-patterned polarizing element having a different polarization axis and a stereoscopic display device using the micro-patterned polarizing element, which enables stereoscopic viewing.

[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 Conferance, a resist is coated on the stretched dichroic polyvinyl alcohol film, and after patterning, 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 stacked. A method of manufacturing a polarizing element called μPol and using it for stereoscopic viewing has been announced (SID 91 DIGEST
p840-843). 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. Japanese Patent Application Laid-Open No. 9-73015 proposes a micro-patterned polarizing element in which a substrate is coated with a fluororesin alignment film, a resist is applied thereon, and after patterning, a material containing a dichroic dye is laminated. ing. JP-A-10-160
No. 932 proposes a polarizing element in which a plurality of polarizing pieces are attached to a base material with different polarization 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 partial polarizing member cut off with a dicer is used. A polarizing element in which different axes are bonded to each other has been proposed.

On the other hand, various methods have been proposed for stereoscopic viewing of images, and binocular stereoscopic viewing using 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
In DIGEST p840-843, USP5327285), a resist is coated on a stretched dichroic polyvinyl alcohol film, and after patterning, the remaining polarizing element part swells when dissolved and removed with an aqueous solution of caustic soda to reduce the polarizing ability. Since two types of substrates whose polarization axes are orthogonal to each other are bonded and manufactured, there is a problem that extremely high positioning accuracy is required at the time of bonding.

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
FM), the part where the dye was uniformly oriented,
A portion (crater) where almost no dye is present and orientation is observed. The absorbance of the part where the dye is uniformly oriented and the part where the dye is hardly present and where the dye is not oriented are measured with a microspectrophotometer.The number of craters reduces the uniformity of the entire dye film and the polarization ability is insufficient. It turned out that it had become something. When the present inventors calculate the dichroic ratio (DR) from the absorbances of the oriented portion and the non-oriented portion, they are as large as DR (a) ≒ 30 and DR (b) ≒ 1.3. There is a difference, and in a larger area including these, DR = 5 to 6
This was not a satisfactory level for a display element. The dichroic ratio (DR) is calculated 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 the substrate with a fluororesin alignment film, applying a resist on it, patterning and then laminating a material containing a dichroic dye to form a micropatterned polarizing element. In the case of the development, the orientation of the fluorine resin alignment film is reduced by the influence of the resist film remaining thin on the surface even after the development or the influence of the development processing, or the orientation of the dichroic dye material laminated on it However, there is a problem that the polarization ability is insufficient and 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. A polarizing element is formed by bonding materials having different transmission axes. However, extremely high precision is required for the step of cutting with a dicer, or 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 the above viewpoint, the present inventors provide a method for producing 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. The present inventors have intensively studied for the purpose and arrived at the present invention. The present invention provides a method disclosed in Japanese Patent Application Laid-Open No. Hei 7-261024, in which the generation of a portion (crater) in which a dye hardly exists and is not oriented is reduced as much as possible, and the orientation of the dichroic compound is increased as a whole. The present invention relates to a method for manufacturing a polarizing element at a practical level for a display element.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies on a photoactive molecular layer and a coating method of a dichroic molecule solution which are more suitable for micropatterned anisotropic arrangement of dichroic dye molecules. , Liquid crystalline polycondensation polymers such as polyamides, polyimides, and polyesters with photoactive groups, liquid crystalline polyaddition polymers such as polyurethane, and liquid crystalline polymers such as liquid crystalline polyvinyl cinnamate It has been found that it shows excellent performance. In the present invention, a liquid crystalline polymer thin film having a photoactive group is used as an alignment film, and the thin film is irradiated with linearly polarized light, and then irradiated with linearly polarized light having a different polarization axis through another micro-patterned mask.
In the step of arranging dichroic molecules on the thin film in a micropattern, a manufacturing method of applying a dichroic molecule solution in such a manner that a specific range of pressure is applied to the substrate in a vertical direction provides high resolution and high light. It has become possible to obtain a micro-pattern polarizing element having extremely large contrast between patterns having different axes.

That is, the present invention provides (1) a method of forming a liquid crystalline polymer thin film having a photoactive group on a substrate, irradiating the thin film with linearly polarized light, and then applying a different micropatterned mask through another mask. After irradiating linearly polarized light having a polarization axis, in the step of arranging dichroic molecules on the thin film in a micropattern, 0.01 MPa ~ in the direction perpendicular to the substrate
A method for manufacturing a polarizing element, in which a dichroic molecule solution is applied so that a pressure of 1.0 MPa is applied, (2) the dichroic molecule solution is
The method for producing a polarizing element according to (1), which is a solution containing an anionic surfactant, wherein the anionic surfactant in (3) and (2) is sodium polyoxyethylene lauryl ether sulfate or polyoxyethylene alkyl ether sulfate. One or more selected from the group consisting of sodium, polyoxyethylene alkyl ether triethanolamine sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, and triethanolamine lauryl sulfate (2) (4) The method for producing a polarizing element according to (4).
The photoactive group in (1) to (3) is a non-aromatic N
ＮN, one or more selected from the group consisting of non-aromatic C１C and non-aromatic C ＝ N (1)
To (3) a method for manufacturing a polarizing element,

(5) The liquid crystalline polymer thin film in (1) to (3) is made of polyamide, polyimide, polyester,
(1) The method for manufacturing a polarizing element of (1) to (3), which is a thin film of a polyurethane resin, and (6) the thin film of liquid crystalline polymer in (1) to (3) is a thin film of a polyvinyl cinnamate resin.
To (3) the method for producing a polarizing element, (7) the method for producing a polarizing element according to (1) to (3), wherein the dichroic molecules in (1) to (3) are dyes having lyotropic liquid crystallinity, 8) The method for producing a polarizing element according to (7), wherein the dye having lyotropic liquid crystallinity in (7) is a dye having a hydrophilic substituent, wherein in (9) and (8), the hydrophilic substituent is a sulfonic acid group or a carboxylic acid. (8) the method for producing a polarizing element, which is at least one group selected from the group consisting of a group, an amino group, and a hydroxyl group, and (10) a laser in which irradiation with linearly polarized light in (1) to (3) is polarized. (11) A method for manufacturing a polarizing element using light, wherein (11) a liquid crystal display device having upper and lower substrates opposed to each other, wherein at least one of the substrates is one of (1) to (10). A substrate having the polarizing element according to any one of the above. That the three-dimensional display device, and more.

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 thermophoric 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 has a high degree of orientation of a thin film of the polymer and sufficiently controls the orientation of a lyotropic liquid crystalline dichroic molecular layer formed thereon. It takes advantage of what can be done.

It is known that liquid crystal compounds are aligned by various external fields such as electric and magnetic fields. Orientation by electric and magnetic fields is well known. In addition, the liquid crystal compound is aligned by the flow of the liquid crystal compound itself, which is called a flow alignment. Further, it is known that even when shearing stress is applied, the material is well oriented in the direction of the force. It has been observed that the dichroic molecule solution used in the present invention also undergoes various alignments under the influence of an external stimulus in a lyotropic liquid crystal state. In the present invention, a dichroic molecule solution is applied and arranged in a micropattern, but it has been found that the effects of various external fields that do not meet this purpose must be avoided as much as possible.

[0016]

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 the groups having such a property that the molecular axis orientation of the photoactive group is changed by irradiation with the 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. .

Examples of the non-aromatic group having an N = N bond include an azobenzene group, an azonaphthalene group, a bisazo group,
Examples thereof include an aromatic azo group such as a formazan group, and an azoxybenzene group. Preferable of these groups for example, the following formula -N = N-A-X -OCO (CH 2) P O-p-phe-N = N-B-Y -A-N = N-p-phe- Y (where A and B represent a benzene ring or a naphthalene ring which may have a substituent, X represents a (C ₁ -C ₁₀ ) alkoxy group or a di (C ₁ -C ₃ ) alkylamino group; And the alkyl group in the dialkylamino group may be the same or different, and may be unsubstituted or one or both may be substituted with a cyano group or a hydroxy group, Y is a hydrogen atom, a fluorine atom, a chlorine atom, Nitro, cyano,
(C ₁ ~C ₁₀₎ alkyl group, (C ₁ ~C ₁₀₎ alkoxy, (C ₁ ~C ₄₎ alkyloxycarbonyl vinyl group,
It represents mono- or di (C ₁ ~C ₃₎ alkylamino group, respectively, the mono- or di (C ₁ ~C ₃₎ alkyl group of the alkyl amino group may be either substituted or unsubstituted, print (C ₁ -C ₃ ) In the case of an alkylamino group, the two alkyl groups may be the same or different. Examples of the substituent on the alkyl group include a cyano group and a hydroxy group. Examples of the mono or di (C ₁ -C ₃ ) alkylamino group substituted with a cyano group or a hydroxy group include a dihydroxyethylamino group, a hydroxy (C ₁ -C ₃ ) alkylamino group, a dicyanoethylamino group, and a cyanoethyl (C ₁ To C ₃ ) alkylamino groups and the like. Also p
Represents an integer of 1 to 10, phe represents a benzene ring,
p-phe or o-phe indicates that it is bonded to an adjacent atom at the para or ortho position. )).

Examples of the group having a non-aromatic C ＝ C bond include groups of polyene, stilbene, stilbazole, stilbazolium, cinnamic acid, isidigo, thioindigo, hemithioindigo and the like. Preferred examples of these groups include, for example, the following formula: —CHＣＨC (X ₁ ) (X ₂ ) (wherein one of X ₁ and X ₂ represents a hydrogen atom, and the other may have a substituent. A 6-membered group ring, a (C ₁ -C ₃ ) alkoxycarbonyl group, or a group in which X ₁ and (X ₂ ) are bonded and represented by —S-o-phe-CO—.
-Phe has the same meaning as described above, and may have a substituent. Examples of the substituent on the aromatic 6-membered ring and the phe group include those described for Y above. )). As the aromatic 6-membered ring, for example, a benzene ring which may have a substituent such as Y or the like,
Examples thereof include a pyridine ring bonded to the C group, and the pyridine ring may be substituted on the nitrogen atom by an alkyl group having 1 to 10 carbon atoms.

As a group having a non-aromatic C = N bond
Include aromatic Schiff bases, aromatic hydrazone groups, etc.
The following formula -NH-N = C (X_Three) (X_Four) -N = CH-BY-A-CH = N-p-phe-Y (wherein X_ThreeAnd X₄Is a hydrogen atom or lower alkoxy
A carbonyl group, the other being a group represented by -BY or
Represents a lower alkoxycarbonyl group, or X _ThreeAnd X_Four
Are bonded to form -CH = NN (lower alkyl) -C
It represents a group represented by O-. A, B, Y, p-ph
e and the like have the same meaning as described above. And the like)
Can be

The wavelength of light absorbed by the liquid crystalline polymer having a photoactive group is not limited to the wavelength in the visible light range but also in the ultraviolet and infrared ranges. When a thin film of a liquid crystalline polymer having a photoactive group is irradiated with linearly polarized light including the wavelength range absorbed by the compound, the molecular axis alignment easily changes.

As the liquid crystalline polymer having a photoactive group used in the present invention, for example, a liquid crystalline polycondensation polymer such as a polyamide, a polyimide and a polyester to which a photoactive group is bonded, or a photoactive group is bonded. 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 type, 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. Specific examples of the liquid crystalline polymer compound include the following compounds.

The following general formula (1)

[0025]

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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-B
-Y

(Wherein A is an optionally substituted ben
X represents a (C) ring or a naphthalene ring; ₁~ C_Ten) Al
Coxy group or di (C₁~ C_Three) Represents an alkylamino group,
Even if the alkyl groups in the dialkylamino group are the same,
It may also be different and unsubstituted or one or both
May be substituted with a cyano group or a hydroxy group
No. Also X₁And X_TwoIndicates a hydrogen atom on one side and the other
An aromatic 6-membered ring optionally having a substituent, (C₁~ C_Three) Arco
Represents a xycarbonyl group, or X₁And X_TwoAre combined,
It represents a group represented by -S-o-phe-CO-. Also,
X_ThreeAnd X_FourIs a hydrogen atom or a lower alkoxycarbohydrate
A lower group, or a group represented by -BY.
Represents a alkoxycarbonyl group, or X_ThreeAnd X_FourBoth
Is bonded to form -CH = NN- (lower alkyl) -CO-
Represents a group represented by Further, even if B has a substituent,
A good benzene ring or naphthalene ring, Y is a hydrogen atom,
Nitrogen atom, chlorine atom, nitro group, cyano group, (C₁~ C
_Ten) Alkyl group, (C₁~ C_Ten) Alkoxy group, (C₁~
C_Four) Alkyloxycarbonyl vinyl group
Is di (C₁~ C_Three) Represents an alkylamino group,
Kuhaji (C₁~ C_Three) The alkyl group of the alkylamino group is
Substituted or unsubstituted, and di (C₁~ C_ThreeA)
In the case of a alkyl group, the two alkyl groups are the same
May be. The substituent on the alkyl group is
An ano group or a hydroxy group is exemplified. Cyano group or
Mono- or di- (C₁~ C_Three)
Dihydroxyethylamino as the alkylamino group
Group, hydroxy (C₁~ C_Three) Alkylamino group, disia
A noethylamino group or a cyanoethyl (C₁~ C_ThreeA)
And a alkylamino group. P is an integer of 1 to 10.
Represents a number, phe represents a benzene ring, p-phe or
o-phe is bonded to an adjacent atom at the para or ortho position
To indicate that Poria having a partial structure represented by)
Mid compound.

The following general formula (2)

[0030]

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(Wherein R ₁ is an alicyclic or aromatic tetracarboxylic acid residue, 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).

[0032]

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(Where Z ₁ is (fa) Yp-phe-N = N—B _O − (f−b) Yp-phe-N = CH—B _O − (fc) Y-p-phe-CH = N-B O - (f-d) (X 1) (X 2) CH = CH-B- represents a group represented by, B _O and B or -C ₆ H ₄ O (CH ₂ )
_P COO-B- indicates, Y in the formula, p-phe,
The symbols (X ₁ ), (X ₂ ), B and p have the same meaning as described above. Q represents an integer of 2 to 4. ) Or the following formula (g)

[0034]

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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), a polyimide compound having a partial structure represented by the following general formula: (3)

[0036]

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

[0038]

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(Wherein Z has the same meaning as in the above formula (1). R ₄ represents a benzene ring, a naphthalene ring, C ₄ -C _{4)
6 represents a} 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) In the general formula (1), Z is the above (a) -N = N
-AX or (e) -OCO (CH ₂ ) _P Op-p-
A polyamide compound having a partial structure wherein phe-N = NBY. (2) In the general formulas (2) and (3), a polyimide compound or a polyurethane compound having a partial structure in which Z ₁ in (f) or (g) is Yp-phe-N = NA-. (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, liquid crystalline polycondensation polymers such as the polyamide compounds, polyimide compounds and polyester compounds of the above (1) to (3) and liquid crystalline polyaddition polymers such as polyurethanes include photoactive groups. Is prepared, and the other functional monomer is reacted in an equimolar amount to obtain a desired liquid crystalline polymer (homopolymer). When producing a copolymer, the desired copolymer is formed by using the same type of bifunctional monomer having no photofunctional group together with the bifunctional monomer having a photoactive group, and reacting in an equimolar manner as described above. A liquid crystalline polymer 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. The other bifunctional monomer having no photoactive group to be reacted with the bifunctional monomer having a photoactive group includes, for example, 4,4′-diamino-3,5,3 ′, 5′-tetraR-substituted Examples thereof include diphenylmethane (R has the same meaning as in the general formula (1)), an alicyclic or aromatic tetracarboxylic acid, and an aliphatic dicarboxylic acid having 2 to 8 carbon atoms. 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 carboxy groups or an aromatic ring or a condensed ring having 8 to 10 carbon atoms, with or without a bridging group 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 liquid crystalline vinyl cinnamate homopolymer (4) can be obtained by polymerizing a vinyl cinnamate monomer. When a copolymer is obtained, a liquid crystalline polymer composed of a desired copolymer can be obtained by polymerizing with a suitable copolymerizable monomer which does not impair liquid crystallinity and has no photoactive group. 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. In order to obtain a copolymer, a monomer having no photoactive group to be copolymerized with a vinyl cinnamate monomer is, for example, 4- (4′-n-pentylphenyl)
Styrene, 4- (4'-n-hexylphenyl) styrene, 4- (4'-n-pentylcyclohexyl) styrene, 4- (4'-n-hexylcycliclehexyl) styrene and the like can be mentioned.

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 amount. Depending on the structure of the body, it ranges from 1: 0 to 1: 100, more preferably from 1: 0 to 1:50.

The polymerization reaction comprises a polyamide compound, a polyimide compound, a polyurethane compound or a polyester compound,
According to a conventionally known method for obtaining a polyvinyl cinnamate polymer, a solution polymerization method or the like in a normal solvent may be used.

The degree of polymerization and the like of the liquid crystalline polymer having a photoactive group used in the present invention obtained as described above are not particularly limited, and vary 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 about 10 or more and about 10,000.

The bifunctional monomer having a photoactive group includes
For example, orthophthalic acid having a photoactive group on a benzene ring, di [amino (C ₂ -C ₄ ) alkyl] amine in which a nitrogen atom substituted with two alkyl groups is further substituted with a photoactive group, and the like. No.

Specific examples of the bifunctional monomer having a photoactive group which is used 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

[0049]

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[0050]

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[0051]

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Monomer suitable for polyimide compound or polyurethane compound

[0053]

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[0054]

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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

[0056]

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Monomer suitable for polyimide compound or polyurethane compound

[0058]

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

[0060]

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Monomer suitable for polyimide compound or polyurethane compound

[0062]

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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 glass substrate or a plastic substrate such as polycarbonate or polyester is used as the substrate), a spin coating method is used. Is preferred. 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 from 0.001 to 5 μm, preferably from 0.01 to 1 μm. When these thin 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 is the type of the liquid crystalline polymer, degree of polymerization, coating method,
Since the appropriate concentration varies depending on the desired film thickness and the like, it cannot be unconditionally determined, but is usually about 0.1% by weight to 10% by weight.
Preferably it is about 0.5% by weight to 5% by weight. An appropriate concentration can be easily determined by performing preliminary tests on the coating method to be used. The solvent used is not particularly limited as long as it dissolves the liquid crystalline polymer, but pyridine, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone, dimethylacetamide,
An aprotic polar solvent such as dimethylimidazoline is a preferred example.

As a method of irradiating a thin film of a liquid crystalline polymer having a photoactive group provided on a substrate with linearly polarized light, various known methods can be applied. In order to manufacture a micropattern polarizing element, it is necessary to print a polarizing pattern on a liquid crystalline polymer thin film having a photoactive group, and for that 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 0.1 mJ / cm
A range from ² to 10 J / cm ² is preferred. 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. If one polarizing element (plate) having a complicated pattern is manufactured, the polarizing element (plate) having a complicated pattern, which has been conventionally difficult, can be straightened by using the polarizing element (plate) as a mask pattern. A large number can be produced by a simple method called polarized light irradiation.

The dichroic dye molecules are simply applied in a micropattern to the thus obtained liquid crystalline polymer thin film having photoactive groups whose molecular axes are arranged in a certain direction, that is, the thin film is coated 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. 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.

The dichroic dye solution used in the present invention has such a property that when a shear stress parallel to the substrate is applied during coating, the solution is easily oriented in the direction of the stress. Even on a substrate on which an alignment latent image for optical alignment was prepared, the alignment control force due to the shear stress exceeds the optical alignment control force in the part where shear stress was applied during the application of the dichroic dye solution. It turned out that the micro pattern of the photo alignment became invisible. Therefore,
It was found that how to reduce the shear stress parallel to the substrate at the time of coating is an important technology in order to realize the orientation of the micro pattern by giving priority to the optical alignment regulating force. That is, a liquid crystalline polymer thin film having a photoactive group is used as an alignment film, the thin film is irradiated with linearly polarized light, and then irradiated with linearly polarized light having a different polarization axis through another micro-patterned mask. In the step of arranging dichroic molecules on the thin film in a micropattern, a shear stress parallel to the substrate is not applied, and 0.01 MPa to 1.0 MPa in the vertical direction.
a, preferably, a micropattern polarizing element having high resolution and extremely high contrast between patterns having different optical axes is obtained by a manufacturing method of applying a dichroic molecule solution so that a pressure of 0.05 MPa to 0.5 MPa is applied. Became possible. Coating methods that are advantageous in controlling such pressure include roll coater coating, flexographic printing,
There are screen printing, curtain coater coating, spray coater coating, etc., and roll coating, curtain coater coating, spray coater coating and the like are particularly preferable.

The dichroic dye (molecule) solution used in the present invention exhibits liquid crystallinity in a certain concentration and temperature range. Certain surfactants have been shown to enhance the nematic liquid crystallinity of dichroic dye solutions. The dichroic dye which is an aromatic compound has a column laminated structure in the liquid crystal phase. It is known that a surfactant also exhibits a lyotropic liquid crystal phase, but often takes a phase different from the lyotropic liquid crystal phase of an aromatic compound. Therefore, when the concentration of the dichroic dye solution containing the surfactant becomes high, the dye liquid crystal phase and the surfactant liquid crystal phase undergo phase separation, and a region containing only the surfactant containing no dye is generated. This phenomenon is observed as a dye-free pinhole in the coating film of the dichroic dye solution, which is remarkably improved by a surfactant, particularly an anionic surfactant. Preferred among the anionic surfactants are polyoxyethylene alkyl ether sulfates, preferably alkali metal salts or lower alkanolamine salts, such as sodium polyoxyethylene lauryl ether sulfate (Emal 20C, Emal E-27C, Emal E-E). 70C and the like: All trade names: Kao Corporation) and other sodium polyoxyethylene alkyl ether sulfates such as Emar 20CM, Levenol WX, Latemul WX, etc. (all trade names: Kao Corporation), poly Oxyethylene alkyl ether triethanolamine sulfate (Emal 20T (trade name), manufactured by Kao Corporation),
Polyoxyethylene alkyl phenyl ether sulfate,
Preferably, an alkali metal salt such as sodium polyoxyethylene alkyl phenyl ether sulfate (Emal N
C-35, Lebenol WZ, etc., all of which are trade names: Kao Corporation), lauryl sulfate, preferably alkali metal lauryl sulfate, ammonium salt or lower alkanolamine salt, for example, sodium lauryl sulfate (Emal 10, Emal 0, etc.) , Manufactured by Kao Corporation), ammonium lauryl sulfate (Emal AD-25R, Emal AD-2)
5, etc., all of which are trade names: Kao Corporation), triethanolamine lauryl sulfate, higher alcohol sulfates, preferably alkali metal sulfates of higher alcohols, such as higher alcohol sodium sulfate (Emal 40 powder (trade name), etc.) Kao Corporation). A liquid crystalline polymer thin film having a photoactive group was used as an alignment film, the thin film was irradiated with linearly polarized light, and then irradiated with linearly polarized light having a different polarization axis through another micro-patterned mask. In the step of arranging dichroic molecules in a micropattern form, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, triethanolamine polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, A dichroic dye solution containing one or two or more surfactants selected from sodium lauryl sulfate, ammonium lauryl sulfate, and triethanolamine lauryl sulfate is applied so that shear stress parallel to the substrate is not applied. Depending on the manufacturing method, the resolution Contrast between different patterns of high optical axis it is possible to obtain a very large micro-pattern polarizing element. A preferable amount of the surfactant is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight in the dichroic dye solution.

As the solvent for dissolving the dichroic dye, water,
Alcohols, ethers, pyridine, dimethylformamide (DMF) / dimethylsulfoxide (DMS
O) · N-methylpyrrolidinone (NMP) · dimethylacetamide (DMAC) · dimethylimidazoline (DM
Aprotic polar solvents such as I) 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% by weight, particularly preferably 0 to 50% by weight. The concentration of the preferred dichroic dye is usually 30% by weight or less, preferably 20% by weight or less, more preferably about 15% by weight or less, based on the entire dichroic dye solution.
% By weight, preferably 0.5% by weight or more, more preferably 0.8% by weight or more. 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 solvent composition, dye type, dye concentration,
The temperature is determined by the coating film thickness, etc.
Preferably, the temperature is 5 to 50 ° C. and the humidity is about 20 to 80% RH, preferably about 40 to 70% 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.

Examples of the dichroic dye include 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 and CIDirectBlue 1
5, CIDirect Blue 67, CIDirect Blue 78, CI
Direct Blue 83, CIDirect Blue 90, CIDirect Blu
e 98, CIDirect Blue 151, CIDirect Blue 168,
CIDirect Blue 202, CIDirect Green 51, CI
Direct Green 59, CIDirect Green 85, CIDirect
Vioet 9, CIDirect Vioet 48, CIDirect Red 2,
CIDirect Red 39, CIDirect Red 79, CIDire
ctRed 81, CIDirect Red 83, CIDirect Red 89,
CIDirect Orange 39, CIDirect Orange 41, CI
Direct Orange 49, CIDirect Orange 72, CIDire
ct Yellow 12, CIDirect Yellow 26, CIDirect Y
ellow 44, CIDirect Yellow 50, CIAcid Red 3
7, CINo.27865, CINo.27915, CINo.27920,
CINo.29058, CINo.29060, disufoindanthrone,
disulfo-N, N'-dixylylperylenetetracarbodiimide and the like. Next, some specific examples are shown below with structural formulas.

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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.
Further,% means% by weight unless otherwise specified.

Example 1 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation of Linearly Polarized Light 2 parts of the following polyamide compound (1) purified product was 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 100 ° C. for 2 hours. Using an ultra-high pressure mercury lamp (500 W / hr), make visible light with a 500 nm cut-off filter, make it linearly polarized through a polarizing plate, and irradiate the film surface of the glass substrate on which the polyamide thin film is formed from a distance of 50 cm for 1 minute. Then, the molecular axis of the photoactive group in the polarized light irradiation part is arranged in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 5 parts of CIDirect Blue 67 and 0.2 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) were added to deionized water 9
Heat and dissolve in 4.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.3 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention. FIG. 1 shows the visible absorption spectrum. The dichroic ratio at the maximum absorption wavelength was 25.

Synthesis of Polyamide Compound (1) 3.1 parts of 5- (4′-dimethylaminophenylazo) isophthalic acid and 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 resulting crystals are filtered, washed with water and dried to obtain polyamide compound (1) (polydiiminor 5- [4- (dimethylamino) phenylazo] isophthaloylimino-1,4- (3,5-diethyl) phenylene methylene-1 , 4- (3,5-diethyl) phenylene {) 5.9 parts. Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Synthesis of 5- (4′-dimethylaminophenylazo) isophthalic acid used as a starting material for polyamide compound (1) 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 2 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation with Linearly Polarized Light 2 parts of the following polyamide compound (2) purified product was 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 applied to the film surface of the glass substrate on which the polyamide thin film was formed at a distance of 50 cm for 1 minute to adjust the molecular axis of the photoactive group in the polarized light irradiation portion. They are arranged in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 1 5 parts of CIDirect Blue 67 and 0.2 parts of Emar 20C (anionic surfactant: manufactured by Kao Corporation) were added to deionized water 9
Heat and dissolve in 4.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Preparation of Associative Dichroic Dye Film 2 1 part of Benzopurpurine 4B and 0.2 part of Emulgen 108 (Nonionic surfactant: manufactured by Kao Corporation) in deionized water 9
Heat and dissolve in 8.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped 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 polyamide compound (2) 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, and the polyamide compound (2) (polydiiminor 5-[(4-dimethylaminophenylazo) phenoxyundecanoloxy] isophthaloyliminol 1,4- (3,5-diethyl) ) Phenylene methylene-1,4- (3,5-dimethyl) phenylene {) 8.7 parts are obtained. Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Synthesis of 5- (4 ′-(4 ″ -dimethylaminophenylazo) phenoxyundecanoyloxy) isophthalic acid used as a starting material for polyamide compound (2) 4-oxy (4′-dimethylaminophenylazo) 8.5 parts of 4- (4′-dimethylaminophenylazo) phenoxyundecanoic acid synthesized from benzene and 11-bromoundecanoic acid and 9.6 parts of thionyl chloride are stirred and reacted in 30 parts of toluene at room temperature for 5 hours. Excessive thionyl chloride is distilled off under reduced pressure, and while cooling with ice water, 7.5 parts of ditetrapyranyl 5-oxyisophthalate and 20 parts of DMF in which 9.6 parts of pyridine are dissolved are added dropwise. After completion of the reaction, the reaction mixture was diluted with 500 parts of a 2% aqueous sodium carbonate solution, and 100 parts of toluene was added, followed by liquid separation. The ene layer was washed with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure to obtain an oil, which was dissolved in 100 parts of dioxane, 10 parts of concentrated hydrochloric acid was added, and the mixture was stirred and reacted to hydrolyze the ester group. Neutralized with an aqueous solution, the precipitated crystals are filtered, washed with water and dried, to give 5- (4 '-(4 "-dimethylaminophenylazo).
A crude product of phenoxyundecanoyloxy) isophthalic acid is obtained. Recrystallization with alcohol gives a purified product.

Example 3 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation with Linearly Polarized Light 2 parts of the purified polyamide compound (2) obtained in Example 2 was dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 1, and 50 cm was formed on the surface of the glass substrate on which the polyamide thin film was formed.
The linearly polarized light is irradiated from the distance of 1 minute for one minute to arrange the molecular axes of the photoactive groups in the polarized light irradiation part in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 10 parts of CIDirect Blue 67 and 0.2 parts of Emar NC (anionic surfactant: manufactured by Kao Corporation) were added to deionized water 8
Heat and dissolve in 9.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.5 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Separate synthesis method of polyamide compound (2) 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 solution of sodium carbonate and distilling off toluene, the precipitated crystals are filtered, washed with water and dried. The crude polyamide is heated and dissolved in a small amount of NMP, diluted with methanol, and purified by reprecipitation. From the NMR measurement, it was clear that about 50% of the oxy groups were replaced with 4- (4'-dimethylaminophenylazo) phenoxyundecanoyl groups.

Example 4 Separate Method for Synthesizing Polyamide Compound (2) 8.5 parts of 4- (4′-dimethylaminophenylazo) phenoxyundecanoic acid was dissolved in 200 parts of dimethylformamide by heating and cooled to 20 ° C. The poly (imino-5-oxyisophthaloylimino-1,4- (3,
5-Diethyl) phenylene-methylene-1,4- (3,
9.1 parts of 5-diethyl) phenylene) is added and dissolved.
Further, 3.4 parts of 2-chloro-1,3-dimethylimidazolium chloride and 3.4 parts of pyridine were added, and 20-2
Stir at 20C for 20 hours. After the reaction is completed, a small amount of insoluble matter is filtered. The filtrate is diluted with 500 parts of a 2% aqueous sodium carbonate solution, and the precipitated polyamide is filtered, washed with water and dried. The crude polyamide is heated and dissolved in a small amount of NMP, diluted with methanol, and purified by reprecipitation. From this NMR measurement, it was clear that about 90% of the oxy groups were replaced with 4- (4'-dimethylaminophenylazo) phenoxyundecanoyl groups.

Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation of Linearly Polarized Light 2 parts of the purified polyamide compound (2) obtained by the above synthesis method is dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 1, and 50 c was formed on the surface of the glass substrate on which the polyamide thin film was formed.
Linearly polarized light is irradiated from a distance of m for 1 minute, and the molecular axis of the photoactive group in the polarized light irradiation portion is arranged in a fixed direction. Then
Linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 3 parts of CIDirect Blue 67 and 0.2 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) were added to deionized water 9
Heat and dissolve in 6.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

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 for them. Table 1

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Example 5 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation with Linearly Polarized Light 2 parts of a purified product of the following polyamide compound (3) was 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,
Then, the light was linearly polarized through a polarizing plate.
Then, the molecular axis of the photoactive group in the polarized light irradiation part is arranged in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 3 parts of CIDirect Blue 67 and 0.2 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) were added to deionized water 9
Heat and dissolve in 6.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Synthesis of Polyamide Compound (3) 3.5 parts of 5- (4′-dimethylaminonaphthylazo) isophthalic acid and 50 parts of 4,4′-diamino-
3.1 parts of 3,5,3 ', 5'-tetraethyldiphenylmethane (TEDPM) is added and dissolved by 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 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 resulting crystals are filtered, washed with water and dried, and the polyamide compound (3) (polydiiminor 5- [4- (dimethylamino) naphthylazo] isophthaloylimino-1,
4- (3,5-diethyl) phenylenemethylene-1,4
3.5 parts of-(3,5-diethyl) phenylene｝) are obtained. Heat and dissolve in a small amount of NMP, dilute with methanol and purify by reprecipitation.

Synthesis of 5- (4′-dimethylaminonaphthylazo) isophthalic acid used as a raw material of the above 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, 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 6 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation with Linearly Polarized Light 2 parts of a purified product of the following polyamide compound (4) was dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 1, and an ultra-high pressure mercury lamp (5
00W / hr) and made visible light with a 500 nm cut-off filter, and then linearly polarized light through a polarizing plate.
On the surface of the glass substrate on which the polyamide thin film is formed, 50
Irradiate from a distance of 1 cm for 1 minute to align the molecular axis of the photoactive group in the polarized light irradiation part in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of associative dichroic dye film 1 part of Benzopurpurine 4B and 0.2 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) were added to deionized water 9
Heat and dissolve in 8.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Synthesis of Polyamide Compound (4) 5- (4′-methoxynaphthylazo) was added to 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 resulting crystals are filtered, washed with water and dried, and the polyamide compound (4) (poly [imino 5- (4-dimethoxynaphthylazo) isophthaloylimino 1,4- (3,5
-Diethyl) phenylenemethylene-1,4- (3,5-
Diethyl) phenylene!) 3.5 parts are obtained. Small amount of NM
Heat and dissolve in P, dilute with methanol and purify by reprecipitation.

Synthesis of 5- (4'-methoxynaphthylazo) isophthalic acid used as a raw material for the above polyamide compound (4) 12.6 parts of diethyl 5-aminoisophthalate, 18 parts of 6N hydrochloric acid in 40 parts of water And cool 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 7 Synthesis of Polyimide (1) and Preparation of Thin Film 3.26 parts of 4-dimethylamino-4′-di (amino) ethylaminophenylazobenzene and 60 parts of N-methyl-2-pyrrolidone were fed in four ports. The flask is charged and dissolved with stirring 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 0.6-0.
Spin-coat to 7 μm and heat at 200 ° C. for 1 hour to obtain the polyimide thin film. Ultra-high pressure mercury lamp (5
00W / hr), a 550 nm cut-off filter is used to make visible light, and then linearly polarized light is passed through a polarizing plate. Then, the molecular axis of the photoactive group in the polarized light irradiation part is arranged in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

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) were dissolved in 8.98 parts of deionized water by heating, and a dye solution was prepared. To adjust. This dye solution was applied on the film surface of the polyimide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Example 8 Synthesis of polyimide (2) and preparation of thin film N, N-diaminoethyl-4- (4 '-(4 "-dimethylaminophenylazo) phenoxy) undecanoyloxyaniline 3.01 parts; 60 parts of N-methyl-2-pyrrolidone are charged into a four-necked flask, and stirred and dissolved while blowing with nitrogen under water cooling, and 1.55 parts of 4,4′-oxydiphthalic anhydride is added little by little. Thereafter, the mixture was reacted with water for 4 hours at 60 ° C. for 10 hours to obtain a polyamic acid solution.
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. Using an ultra-high pressure mercury lamp (500 W / hr), 55
0 nm cut-off filter converts the light to visible light, and then makes it linearly polarized through a polarizing plate.
Irradiation is performed for 1 minute from a distance of 0 cm to arrange the molecular axes of the photoactive groups in the polarized light irradiation portion in a fixed direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

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) were dissolved in 8.98 parts of deionized water by heating, and a dye solution was prepared. To adjust. This dye solution was applied on the film surface of the polyimide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Synthesis Examples of Other Polyimides The following diamines and tetracarboxylic anhydrides were reacted according to Examples 7 and 8 to obtain the polyimides shown in Table 2. The same photo-alignment effect can be obtained for them. Table 2

[0109]

[0110]

[0111]

[0112]

[0113]

Example 9 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 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. Are arranged in a certain direction. Next, the linearly polarized light rotated by 90 ° is converted to the light shown in FIG.
Irradiate the film surface of the unexposed portion of the polyamide thin film coated substrate for 1 minute from a distance of 50 cm through a stripe-shaped mask shown in the above, the molecular axis of the photoactive group of the polarized light irradiation portion and the molecular axis Arrange in 90 ° different directions.

Preparation of Associative Dichroic Dye Film One part of CIDirect Blue 1 and one part of CIDirect Blue 67
Department, CIDirect Red 79 0.5 parts, CIDirect Orange
0.5 parts of 39 and 0.2 parts of Emulgen 108 (Nonionic surfactant: manufactured by Kao Corporation) are dissolved in 96.8 parts of deionized water by heating to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. 30 coated substrates
After drying under the conditions of 60 ° C. and 60% RH, the polarization axis of the present invention is 9%.
A polarizing element having a stripe shape different from 0 ° was obtained.

Example 10 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 on 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. Are arranged in a certain direction. Next, the linearly polarized light rotated by 90 ° is converted to the light shown in FIG.
Irradiate the film surface of the unexposed portion of the polyamide thin film coated substrate for 1 minute from a distance of 50 cm through a stripe-shaped mask shown in the above, the molecular axis of the photoactive group of the polarized light irradiation portion and the molecular axis Arrange in 90 ° different directions.

Preparation of Associative Dichroic Dye Film One part of CIDirect Blue 83 and one part of CIDirect Blue 67
Department, CIDirect Red 2 0.5 parts, CIDirect Orange
0.5 parts of 39 and 0.2 parts of Emulgen 108 (Nonionic surfactant: manufactured by Kao Corporation) are dissolved in 96.8 parts of deionized water by heating to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. 30 coated substrates
After drying under the conditions of 60 ° C. and 60% RH, the polarization axis of the present invention is 9%.
A polarizing element having a stripe shape different from 0 ° was obtained.

Example 11 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. Three parts of CIDirect Blue 15 and 0.02 part of Emulgen 108 (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 parts of CIDirect Red 28 and 0.02 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) are dissolved in 6.98 parts of deionized water by heating to prepare a red dye solution. Further
3 parts of CIDirect Green 85 and 0.02 part of Emulgen 108 (nonionic surfactant: manufactured by Kao Corporation) are dissolved in 6.98 parts of deionized water by heating to prepare a green dye solution. This dye solution is striped blue by screen printing method,
Red and green are separately printed on the surface of the polyamide thin film substrate and dried under the conditions of 40 ° C. and 60% RH to obtain the blue, red and green striped polarizing elements of the present invention.

Example 12 Preparation of a photoactive group-containing polyamide thin film and irradiation with linearly polarized light. 2 parts of the purified product of the polyamide compound (1) obtained in Example 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 100 ° C. for 2 hours. Ultra high pressure mercury lamp (50
0 W / hr), a visible light is cut by a 500 nm cut-off filter, and then a linearly polarized light is passed through a polarizing plate.
m is irradiated for 1 minute from a distance of m to arrange the molecular axis of the photoactive group in the polarized light irradiation portion in a fixed direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 5 parts of CIDirect Blue 67 and 0.2 part of Emal E-27C (sodium polyoxyethylene lauryl ether sulfate: anionic surfactant: manufactured by Kao Corporation) were deionized water. Heat and dissolve in 94.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.3 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention. The dichroic ratio at the maximum absorption wavelength was 25.

Example 13 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation with Linearly Polarized Light 2 parts of the purified polyamide compound (2) obtained in Example 2 was dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 12, and 50 c was formed on the surface of the glass substrate on which the polyamide thin film was formed.
Linearly polarized light is irradiated from a distance of m for 1 minute, and the molecular axis of the photoactive group in the polarized light irradiation portion is arranged in a fixed direction. Then
Linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of associative dichroic dye film 1 5 parts of CIDirect Blue 67 and 0.2 parts of Emar E-27C (anionic surfactant: manufactured by Kao Corporation) were heated and dissolved in 94.8 parts of deionized water. A dye solution is prepared. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Preparation of Associative Dichroic Dye Film 2 1 part of Benzopurpurine 4B and 0.2 part of Emar E-27C (anionic surfactant: manufactured by Kao Corporation) were heated and dissolved in 98.8 parts of deionized water. A dye solution is prepared. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention. The dichroic ratio at the maximum absorption wavelength was 30.

Example 14 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation of Linearly Polarized Light 2 parts of the purified polyamide compound (2) obtained in Example 2 was dissolved in 98 parts of NMP to prepare a 2% polymer solution. The polyamide thin film was formed according to Example 12, and 50 c was formed on the surface of the glass substrate on which the polyamide thin film was formed.
Linearly polarized light is irradiated from a distance of m for 1 minute, and the molecular axis of the photoactive group in the polarized light irradiation portion is arranged in a fixed direction. Then
Linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 10 parts of CIDirect Blue 67 and 0.2 part of Emar 20CM (sodium polyoxyethylene alkyl ether sulfate: anionic surfactant: manufactured by Kao Corporation) were mixed with 89 parts of deionized water. Heat and dissolve in 8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.5 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Example 15 Synthesis of Polyamide Compound (2) In the same manner as in Example 4, a polyamide compound (2) was synthesized. From the NMR measurement, it was clear that about 90% of the oxy groups were replaced with 4- (4′-dimethylamino) phenylazophenoxyundecanoyl groups.

Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation of Linearly Polarized Light
Dissolve in 8 parts to make a 2% polymer solution. Example 1
2. The polyamide thin film is formed in accordance with 2 above, and linearly polarized light is irradiated from a distance of 50 cm to the film surface of the glass substrate on which the polyamide thin film is formed for 1 minute, so that the molecular axis of the photoactive group in the polarized light irradiation portion is fixed. Array. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film Deionize 3 parts of CIDirect Blue 67 and 0.2 parts of Emal 20T (polyoxyethylene alkyl ether triethanolamine sulfate: anionic surfactant: manufactured by Kao Corporation) The dye solution is prepared by heating and dissolving in 96.8 parts of water.
This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention. In the same manner as in Example 15, the stripe-shaped polarizing element of the present invention can be obtained also from the above-mentioned polyamide compounds in Table 1.

Example 16 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation of Linearly Polarized Light 2 parts of the purified polyamide compound (3) obtained in Example 5 was 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. Ultra-high pressure mercury lamp (5
00W / hr), a visible light was passed through a 550 nm cut-off filter, and a linearly polarized light was passed through a polarizing plate.
Irradiate from a distance of 1 cm for 1 minute to align the molecular axis of the photoactive group in the polarized light irradiation part in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film 3 parts of CIDirect Blue 67 and 0.2 part of Emal NC-35 (sodium polyoxyethylene alkylphenyl ether sulfate: anionic surfactant: manufactured by Kao Corporation) were deionized. Heat and dissolve in 96.8 parts of water to prepare a dye solution.
This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Example 17 Preparation of Photoactive Group-Containing Polyamide Thin Film and Irradiation of Linearly Polarized Light 2 parts of the purified polyamide compound (4) obtained in Example 6 was 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 12, and the ultra-high pressure mercury lamp (500 W / hr) was used to 500 nm
After making visible light with a cut-off filter and further making it linearly polarized through a polarizing plate, the film surface of the glass substrate on which the polyamide thin film was formed was irradiated for 1 minute from a distance of 50 cm, and the molecular axis of the photoactive group in the polarized light irradiation part Are arranged in a certain direction. Next, linearly polarized light having different polarization axes is similarly irradiated through a stripe-shaped mask to partially arrange the molecular axes of the photoactive groups in different directions.

Preparation of Associative Dichroic Dye Film One part of Benzopurpurine 4B and 0.2 part of Levenol WX (sodium polyoxyethylene alkyl ether sulfate: anionic surfactant: manufactured by Kao Corporation) were mixed with 9 parts of deionized water.
Heat and dissolve in 8.8 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater for a single-wafer substrate. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale.
The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Example 18 Synthesis of Polyimide (1) and Preparation of Thin Film In the same manner as in Example 7, synthesis of polyimide (1) and preparation of a thin film were performed to obtain a polyimide thin film substrate.

Preparation of Associative Dichroic Dye Film One part of CIDirect Blue 67 and 0.02 part of Emal AD-25R (ammonium lauryl sulfate: anionic surfactant: manufactured by Kao Corporation) were added to 8.98 parts of deionized water. Heat and dissolve to prepare a dye solution. This dye solution was applied on the film surface of the polyimide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate is 30 ℃,
After drying under the condition of 60% RH, a striped polarizing element of the present invention was obtained.

Example 19 Synthesis of Polyimide (2) and Preparation of Thin Film In the same manner as in Example 8, synthesis of polyimide (2) and preparation of a thin film were performed to obtain a polyimide thin film substrate.

Preparation of Associative Dichroic Dye Film One part of CIDirect Blue 67 and 0.02 part of Emal E-27C (sodium polyoxyethylene lauryl ether sulfate: anionic surfactant: manufactured by Kao Corporation) were deionized water. Heat and dissolve in 8.98 parts to prepare a dye solution. This dye solution was applied on the film surface of the polyimide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention.

Using polyimides shown in Table 2, Example 1
By forming an associative dichroic dye film according to 8 and 19, the striped polarizing element of the present invention can be obtained.

Example 20 A glass substrate in which linearly polarized light obtained in the same manner as in Example 12 was applied to the polyamide thin film-coated substrate prepared in Example 12 through a stripe-shaped mask shown in FIG. Is irradiated from a distance of 50 cm for 1 minute to arrange the molecular axes of the photoactive groups in the polarized light irradiation portion in a certain direction. Then, 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 axis of the photoactive group is arranged in a direction different from the molecular axis by 90 °.

Preparation of Associative Dichroic Dye Film One part of CIDirect Blue 1 and one part of CIDirect Blue 67
Department, CIDirect Red 79 0.5 parts, CIDirect Orange
0.5 part of 39, Emal 20C (sodium polyoxyethylene lauryl ether sulfate: manufactured by Kao Corporation)
2 parts are heated and dissolved in 96.8 parts of deionized water to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention in which the polarizing axes differ by 90 °.

Example 21 A glass substrate on which the polyamide thin film was formed by applying the linearly polarized light obtained in the same manner as in Example 15 to the substrate coated with the polyamide thin film prepared in Example 15 through the stripe-shaped mask shown in FIG. Is irradiated from a distance of 50 cm for 1 minute to arrange the molecular axes of the photoactive groups in the polarized light irradiation portion in a certain direction. Then, the linearly polarized light rotated by 90 ° was irradiated for 1 minute from a distance of 50 cm onto the film surface of the unexposed portion of the polyamide thin film-coated substrate through a stripe-shaped mask shown in FIG. The molecular axis of the photoactive group is arranged in a direction different from the molecular axis by 90 °.

Preparation of Associative Dichroic Dye Film One part of CIDirect Blue 83 and one part of CIDirect Blue 67
Department, CIDirect Red 2 0.5 parts, CIDirect Orange
Heat 0.5 parts of 39 and 0.2 parts of Emal 20C in 96.8 parts of deionized water to prepare a dye solution. This dye solution was applied on the film surface of the polyamide thin film substrate using a roll coater. The roll coater finely adjusted the position between the coating roll and the substrate in advance and adjusted the pressing pressure between the roll and the substrate to 0.2 MPa. The pressure was measured by Fuji Film Prescale. The coated substrate was dried under the conditions of 30 ° C. and 60% RH to obtain a striped polarizing element of the present invention in which the polarizing axes differ by 90 °.

Example 22 The substrate coated with the polyamide thin film prepared in Example 12 was irradiated with linearly polarized light obtained in the same manner as in Example 12 on the film surface of the glass substrate on which the polyamide thin film was formed for 1 minute from a distance of 50 cm. Then, the molecular axis of the photoactive group in the polarized light irradiation part is arranged in a certain direction.

Preparation of Associative Dichroic Dye Film 3 parts of CIDirect Blue 15 and 0.02 part of Emar 20C (anionic surfactant: manufactured by Kao Corporation) were dissolved in 6.98 parts of deionized water by heating and blue. Prepare a dye solution. next
3 parts of CIDirect Red 28 and 0.02 part of Emar 20C (anionic surfactant: manufactured by Kao Corporation) are dissolved in 6.98 parts of deionized water by heating to prepare a red dye solution. Further
3 parts of CIDirect Green 85 and 0.02 part of Emar 20C (anionic surfactant: manufactured by Kao Corporation) are dissolved in 6.98 parts of deionized water by heating to prepare a green dye solution. This dye solution is striped blue, red,
Each green color is printed on the surface of the polyamide thin film substrate and dried at 40 ° C. and 60% RH to obtain the blue, red and green striped polarizing elements of the present invention.

[0145]

According to the present invention, a polarizing element can be obtained only by arranging dichroic molecules in a micropattern on a liquid crystal resin 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.

[0146]

[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 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. 4 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. 4 is located between the light-shielding portions of FIG. 3.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takashi Tamaki 1-1-1 Higashi, Tsukuba City, Ibaraki Pref. FB02 FC23 GA01 LA12 LA17 LA30 MA01

Claims (11)

[Claims] 1. A liquid crystalline polymer thin film having a photoactive group is formed on a substrate, the thin film is irradiated with linearly polarized light, and then linearly polarized light having different polarization axes is irradiated through another micro-patterned mask. After the irradiation, in the step of arranging the dichroic molecules in a micro pattern on the thin film, a dichroic molecule solution is applied so that a pressure of 0.01 MPa to 1.0 MPa is applied to the substrate in the vertical direction. Manufacturing method of polarizing element 2. The method for producing a polarizing element according to claim 1, wherein the dichroic molecule solution is a solution containing an anionic surfactant. 3. An anionic surfactant according to claim 2, wherein the sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, triethanolamine polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate. 3. The method for producing a polarizing element according to claim 2, wherein the polarizing element is at least one selected from the group consisting of sodium lauryl sulfate, ammonium lauryl sulfate, and triethanolamine lauryl sulfate. 4. The photoactive group according to claim 1, wherein the photoactive group is selected from the group consisting of non-aromatic N = N, non-aromatic C = C, and non-aromatic C = N. 4. The method for manufacturing a polarizing element according to claim 1, wherein the method is one or two or more kinds. 5. The method for manufacturing a polarizing element according to claim 1, wherein the liquid crystalline polymer thin film according to claim 1 is a polyamide, polyimide, polyester or polyurethane resin thin film. 6. A method for manufacturing a polarizing element according to claim 1, wherein the liquid crystalline polymer thin film according to any one of claims 1 to 3 is a polyvinyl cinnamate resin thin film. 7. The method for manufacturing a polarizing element according to claim 1, wherein the dichroic molecules according to any one of claims 1 to 3 are dyes having lyotropic liquid crystallinity. 8. The method for producing a polarizing element according to claim 7, wherein the dye having lyotropic liquid crystallinity according to claim 7 is a dye having a hydrophilic substituent. 9. The method according to claim 8, wherein the hydrophilic substituent is at least one group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, an amino group and a hydroxyl group. 10. The method for manufacturing a polarizing element according to claim 1, wherein the irradiation of the linearly polarized light according to claim 1 is performed using a laser beam having a polarization property. 11. A three-dimensional display device comprising a liquid crystal display device having upper and lower substrates opposed to each other, wherein at least one of the substrates is a substrate having the polarizing element according to claim 1.