JPH112721A - Phase shifter and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phase shifter having two regions; a region positive in retardation and a region negative in retardation in one phase shifter by irradiating part of the regions of an org. high-polymer film subjected to a uniaxial treatment with UV rays or electronic rays. SOLUTION: The regions of the org. high-polymer film subjected to the uniaxial treatment are irradiated with the UV rays or electron rays, by which the region positive in the retardation and the region negative in the retardation are formed on the org. high-polymer film. In such a case, the high-polymer film of which the retardation changes from positive to negative is used when irradiated with the UV rays or electron rays after the film is subjected to an orientation treatment in the direction where the retardation is position. For example, a photosensitive high polymer, such as polyvinyl cinnamate, having an unsatd. bond in a molecular chain is usable as the material for producing such high-polymer film. A dimerization reaction or isomerization reaction occurs in such high polymer by irradiation with the UV rays, by which the direction of the retardation thereof is changed from negative top positive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a retarder and a method for producing the same. In this specification, the term "a retarder" refers to a retardation plate, a wave plate, a liquid crystal element, and a recording element using light. The present invention particularly relates to a retarder having both a positive retardation region and a negative retardation region, and a method for producing the retarder. This method is characterized in that the organic polymer film is irradiated with ultraviolet rays or electron beams. The retarder of the present invention can be applied to a dielectric multilayer film of a polarizing element, a retardation plate for a liquid crystal display, a diffraction grating, a holographic element (for reading a bar code, for a magneto-optical disk head), and the like.

[0002]

2. Description of the Related Art Conventionally, there is a technique of a phase hologram in which two light waves form interference fringes by utilizing the fact that the phases are different. The application range of this technology is wide, and it is used for a hologram, a three-dimensional image display, and the like utilizing a combination of a polarizing plate and a magneto-optical disk head, a bar code reading, and a diffraction grating. For example, hologram is a technology that uses two light waves with different retardation signs to form interference fringes. For this application, technologies such as photoresist and thermoplastic photoconductors are used to make the retardation difference. Is known.
However, these have problems in the process.

Conventionally, a light wavefront direct recording hologram for directly recording interference fringes by a laser beam on a photosensitive material has been often used as a hologram. For this photosensitive material, a photoresist or a thermoplastic photoconductor is generally used. These express a phase difference using a change in the refractive index due to unevenness. When a photoresist is used, a step of rinsing with a solvent or the like after irradiating a laser beam or the like to form a recess is required. Further, in the case of a thermoplastic photoconductor, heat treatment is similarly required after light irradiation.

On the other hand, depending on the application, a liquid crystal can be used as a phase shifter such as a wave plate to adjust the color tone (Japanese Patent Laid-Open No. 9-33901). In this liquid crystal element, positive retardation is generated by rubbing the polymer film with a buff cloth such as nylon in one direction, and liquid crystals are arranged in the direction of the retardation to generate retardation in the positive direction as a liquid crystal element ( JP-A-52-2541).

However, in order to partially change the positive or negative of the retardation, the rubbing direction must be partially changed. That is, a part of the polymer film is covered with a resist film or the like, and is rubbed so as to generate positive retardation. The resist film is peeled off, and another resist film covers the portion where positive retardation is generated, and is rubbed so as to generate negative retardation. 2 by removing the resist film
A film with two directions of retardation is completed. When the liquid crystal is arranged in this film, the liquid crystal is also oriented according to the direction of the retardation of the film. Therefore, this method requires a photolithography technique, and requires a large number of steps and a complicated process. Further, by removing the resist film, the film is damaged and the amount of retardation is attenuated.

[0006]

Therefore, the present invention solves these problems and solves the above problem by providing a retarder having two regions, one having a positive retardation and the other having a negative retardation, in one retarder. An object is to provide a simple manufacturing method thereof.

[0007]

That is, the present invention provides a retarder having optical anisotropy and having a positive retardation region and a negative retardation region. Here, a positive retardation means that the phase is advanced by 0 to 2π, and a negative retardation means that the phase is delayed by 0 to 2π. Preferably, in the phase shifter of the present invention, a region where the retardation is positive on the organic polymer film by irradiating a part of the region of the organic polymer film subjected to the uniaxial treatment with an ultraviolet ray or an electron beam. And a region that is negative. More preferably, the retarder is a device manufactured from an organic polymer film and a liquid crystal.

[0008] The present invention further provides a method of manufacturing a retarder. This method prepares an organic polymer film, performs uniaxial treatment on the organic polymer film, and irradiates a partial region of the organic polymer film with ultraviolet light or an electron beam, thereby forming an organic polymer film on the organic polymer film. And a step of generating a region where the retardation is positive and a region where the retardation is negative.
For example, by applying a uniaxial treatment to the organic polymer film to generate positive retardation, and then irradiating a partial region of the organic polymer film with ultraviolet light or an electron beam, the retardation of the irradiated region is reduced. It is possible to obtain a retarder that has a negative value and the retardation of the non-irradiated area remains positive. In another aspect, the present invention provides a method for manufacturing a retarder that is a liquid crystal device. This method prepares an organic polymer film, performs uniaxial treatment on the organic polymer film, irradiates a part of the organic polymer film with ultraviolet light or an electron beam, and arranges a liquid crystal on the organic polymer film. Assembling the liquid crystal element such that the retardation of the liquid crystal arranged in the non-irradiated area has a positive value, and the retardation of the liquid crystal arranged in the irradiated area has a negative value. It is characterized by the following.

According to another aspect of the present invention, there is provided an organic polymer film characterized in that irradiation of ultraviolet rays or an electron beam causes a negative value of the retardation of the irradiated area. In still another embodiment of the present invention, by irradiating a part of the organic polymer film with ultraviolet light or an electron beam, the retardation of the liquid crystal disposed in the non-irradiated region on the organic polymer film has a positive value. And the retardation of the liquid crystal disposed in the irradiated area on the organic polymer film has a negative value. The organic polymer film according to the present invention preferably comprises a polymer (A) that produces positive retardation by uniaxial treatment and a polymer (B) that produces negative retardation by uniaxial treatment and irradiation with ultraviolet rays or electron beams. .
More preferably, at least one kind of the polymer material contained in the polymer (B) is a polymer compound having a cyclic structure having 4 or more carbon atoms. Also preferably, the polymer (A) is a polyimide, polyamide, polyether, polyester or polyurethane.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a polymer film whose retardation changes from positive to negative when irradiated with an ultraviolet ray or an electron beam after an orientation treatment in a direction in which retardation is positive. As a material for producing such a polymer film, for example, a photosensitive polymer having an unsaturated bond in a molecular chain such as polyvinyl cinnamate can be used. Such polymers are
Irradiation of ultraviolet rays causes a dimerization reaction or an isomerization reaction, and the direction of the retardation changes from positive to negative.

Alternatively, the polymer film used in the present invention is composed of a polymer (hereinafter, referred to as polymer (A)) in which positive retardation is caused by the alignment treatment, and a polymer which is negative by the alignment treatment and irradiation of ultraviolet rays or electron beams. It can be obtained by mixing a polymer with which retardation occurs (hereinafter, referred to as polymer (B)).

When this mixed polymer film is used, the retardation of the polymer (A) is positive and the amplitude is small, and the retardation of the polymer (B) is negative and the amplitude is large depending on the irradiation amount of ultraviolet rays. A combination is preferred. The appropriate combination of the retardations can be adjusted not only by the material properties of the polymer (A) and the polymer (B) but also by the mixing ratio and the irradiation amount of ultraviolet rays or the like.

When a polymer film is used as a phase shifter, the mixing ratio of the polymer (A) and the polymer (B) is 1:20, although it varies depending on the characteristics of the polymer material and the combination of the polymer materials.
And a range of 20: 1. When a liquid crystal element is used as a phase shifter, the ratio varies depending on the characteristics of the polymer material and the combination of the polymer materials. However, the appropriate mixing ratio of the polymer (A) and the polymer (B) is 1:50. And a range of 50: 1.

The polymer (A) and the polymer (B) may each be used in combination of two or more. Alternatively, in the case of a polymer material containing an unsaturated bond in a molecular chain such as polyvinyl cinnamate, only the polymer (B) may be used.

The polymer (A) is not particularly limited, but may be polyimide, polyamide, polyether,
Main chain polymers such as polyester and polyurethane are preferred. Preferably, they are polyimide and polyamide. More preferably, polyimide or polyamide containing fluorine or a siloxane group is preferable.

The polymer (B) is not particularly restricted but includes, for example, polystyrene, polycyclohexyl methacrylate, polyvinyl anthracene, polyvinyl norbornene, polyvinyl butyl styrene, polycyclohexyl acrylate, polyacenaphthylene, polyvinyl diphenyl, Polyvinyl naphthalene, polyvinyl formal, polyphenyl methacrylate, polyvinyl toluene, polyvinyl pyridine, polyvinyl pyridine-
N-oxide, polyvinyl carbazole, polyvinyl methyl ketone, polyvinyl pyridine-divinyl benzene, polyvinyl (1-methoxy) -p-carboxyphenyl carbaldehyde, polyvinyl chloroacetate, polyvinyl acetate, polyvinyl benzyl chloride,
Polyvinylimidazole, polyvinylphthalimide, polyvinylbenzoic acid, polyvinylaminobenzene, polyvinylphenol, polyvinylcyclohexylamine, polyvinylnaphthylamine, polyvinylbenzylamine, polyvinyldimethylcyclohexylamine, polyvinylphenylquinolinamine, polyvinylquinolinecarboxamide, polyvinylbenzylhexafluoroisopropyl ether , Polyvinyl-β-carboline, polyvinylsinoline, polyvinylquinazoline, polyvinylpurine, polyvinylisoquinoline, polyvinylquinoline, polyvinylinoxaline, polyvinylphthalazine, polyvinylnaphthyridine, polyvinylisoindole, polyvinylindole, polyvinylpyridazine, polyvinyloxolane, Ribiniru-2-furaldehyde,
Polyvinylinden-1-one, polyvinylfluoren-9-one, polyvinyl-2-pyridone, polyvinyl-
2-quinolone, polyvinyl-9-carbonylfluorene, polyvinylthiophene, polyvinylacridine, polyvinylphenylpyridine, polyvinylfluorophenylpyridine, polyvinylfluorobenzene, polyvinylfluoromethylbenzene, polyvinyl-o-trifluoromethylaniline, polyvinylpentafluorobenzene, polyvinyl Methylcarbamoylbenzene, polyvinylcarbamoylimidazole, polyvinylchlorobenzene, polyvinylnitrobenzene, polyvinylnitronaphthalene, polyvinylaminonaphthalene, polyvinylsulfobenzene, polyvinylaminopyridine, polyvinylcarboxypyridine, polyvinylhydroxybenzene,
Polyvinyl formylbenzene, polyvinylaminoethylbenzene, polyvinylhydroxymethylbenzene, polyvinyltrifluoroethylbenzene, polyvinylmethoxyaminobenzene, polyvinyl-4-amino-tetrafluoropyridine, polyvinyldifluoromethylbenzene, polyvinyldifluorobenzene, polyvinylmethoxybenzene, polyvinylaminocyclohexane , Polyvinylaminocyclopentane, polyvinylcyclohexanecarboxylic acid, polyvinylhydroxycyclohexane, polyvinylfluoromethylcyclohexane, polyvinylcyanocyclohexane, polyvinylformylcyclohexane, polyfluorostyrene, polydifluorostyrene, polytrifluorostyrene, polytetrafluorostyrene, polypentane Ruorosuchiren, poly trifluoromethyl styrene, polybis (trifluoromethyl styrene), polyvinyl norbornyl methacrylate, polyvinyl isobornyl, polydiene cyclopentenylene b methacrylate, polyvinyl dioxazine run, poly methoxystyrene, and the like.

Polyacrylate or polymethacrylate in which the vinyl group in the polyvinyl compound is replaced with an acryl or methacryl group is also a specific example of the polymer (B).

In the present invention, preferably, the polymer (B)
May be at least partially containing a monomer unit having a bulky group, and may be a homopolymer or a copolymer with another monomer unit.

Examples of the monomer unit include β-carboline, sinoline, quinazoline, purine, isoquinoline,
Quinoline, quinoxaline, phthalazine, naphthyridine,
Isoindole, indole, pyridazine, oxalan, 2-furaldehyde, inden-1-one, fluoren-9-one, 2-pyridone, 2-quinolone, 9-carbonylfluorene, thiophene, acridine, phenylpyridine, fluorophenylpyridine, fluoro Benzene, fluoromethylbenzene, o-methoxybenzaldehyde, cyanobenzene, methylcarbamoylbenzene, carbamoylimidazole, benzoic acid, chlorobenzene, nitrobenzene, nitronaphthalene, aminobenzene, aminonaphthalene, sulfobenzene, aminopyridine, carboxypyridine, hydroxybenzene , Fluoromethylpyridine, formylbenzene, aminoethylbenzene, hydroxypyridine, hydroxymethylbenzene, trifluoro Ethylbenzene, cyanoethylbenzene, formylethylbenzene, methoxyaminobenzene, 4-amino-tetrafluoropyridine, difluoromethylbenzene, difluorobenzene, methoxybenzene, aminocyclohexane, fluoromethylcyclohexane, cyanocyclohexane, aminocyclopentane, cyclohexanecarboxylic acid, hydroxy -COO groups such as cyclohexane linked by a direct bond from or vinyl chain vinyl chain _{-, - OCH 2 -, -} OCO
—, —CH ₂ —, —C ₂ H ₅ — and a non-polarizable cyclic hydrocarbon, for example, a monomer unit bonded to phenylene, naphthylene, cyclohexylene, cyclopentylene and the like.

As the polymer film, one or more of the above-mentioned polymer materials may be used.

The molecular weight of this polymer material is 1,000
0 to 900,000 is preferred. More preferably 10,
It has a molecular weight of 000-500,000.

The irradiation amount of ultraviolet rays or the like is 0.01 m
J to 50J are preferred. More preferably, 0.1 m
J to 10J. The wavelength of ultraviolet light or the like is preferably from 150 to 450 nm, and more preferably from 180 to 400 nm.

When the phase shifter of the present invention is an organic polymer film, for example, the polymer material is uniaxially stretched into a plate having an appropriate thickness, for example, a thickness of several tens μm to 1 cm. It can be manufactured by irradiating a part with an ultraviolet ray or an electron beam. At this time, when irradiating ultraviolet rays or the like, the plate made of this polymer material may be heated to such an extent that the uniaxial orientation by stretching is not disturbed.

When the phase shifter of the present invention is a liquid crystal element, a polymer thin film is formed on a glass substrate with a transparent electrode or on a plastic substrate by spin coating, dipping or printing, and after alignment treatment, ultraviolet light is applied. Alternatively, it can be manufactured by irradiating an electron beam, disposing a liquid crystal on the thin film and assembling a liquid crystal element. The alignment method is not particularly limited, but a rubbing method is preferable.

By using a mask when irradiating an ultraviolet ray or an electron beam, a positive or negative retardation region can be formed. These regions can be arbitrarily changed in size and shape depending on the shape of the mask used.

[0026]

The present invention will be described in more detail with reference to the following examples, which do not limit the present invention. In the following examples, the retardation of the organic polymer film was determined by measuring the anisotropy of the refractive index using an ellipsometer, and the retardation of the liquid crystal element was obtained by using a Berek compensator to obtain the position of the subtraction. Determined by

Example 1 Polyaramid silicone and polyvinyl acenaphthylene were dissolved at a ratio of 1: 3 in n-methylpyrrolidone (NMP) at 3 wt%, and this was dissolved in ITO.
It was applied on a substrate provided with electrodes by a spin coating method. Spin coating was performed at a rotation speed of 2000 r.p.m. p. m. For 20 seconds. This substrate was dried at 180 ° C. for one hour. Thereafter, a rubbing process is performed on the substrate, and one size of a portion that transmits ultraviolet light is 500 μm × 500 μm,
UV light was irradiated for 3 minutes under a 105 W high-pressure mercury lamp using a mask in which the space between adjacent transmission portions was blocked by a material that does not transmit UV light of 500 μm × 500 μm. The two substrates are opposed to each other so that the rubbing directions are parallel to each other and the masked portions are opposed to each other so that the film is disposed inside, and the cell gap 5 is set.
A μm liquid crystal cell was assembled. Liquid crystal (LIXON5047LC manufactured by Chisso Corporation) was injected into the cell, and heat treatment was performed at 110 ° C. When the retardation of this cell was measured, it was found that the portion not irradiated with ultraviolet rays had a positive retardation, and the portion irradiated with ultraviolet rays had a negative retardation.

Example 2 Polyaramide silicone and polyvinyl pyridine were dissolved at a ratio of 1: 4 in NMP at 3 wt%, and the solution was applied on a substrate provided with an ITO electrode by a spin coating method. Spin coating was performed at a rotation speed of 2000 r.p.m.
p. m. For 20 seconds. This substrate was dried at 180 ° C. for one hour. Thereafter, a rubbing treatment is performed on this substrate, and one size of a portion that transmits ultraviolet light is 500 μm.
× 500 μm, 500 μm between adjacent transmission parts
The film was irradiated with ultraviolet light for 3 minutes under a 105 W high-pressure mercury lamp with a mask of mx 500 µm blocked by a material that does not transmit ultraviolet light. A liquid crystal cell with a cell gap of 5 μm was assembled with the two substrates facing each other so that the rubbing directions were parallel to each other and the masked portions faced each other so that the films were arranged inside. Liquid crystal (LIXON5047LC manufactured by Chisso Corporation) was injected into the cell, and heat treatment was performed at 110 ° C. When the retardation of this cell was measured, it was found that the portion not irradiated with ultraviolet rays had a positive retardation, and the portion irradiated with ultraviolet rays had a negative retardation.

Example 3 Polyvinylcinnamate was converted to N
It was dissolved in MP at 3 wt%, and this was applied on a substrate provided with an ITO electrode by a spin coating method. Spin coating was performed at a rotation speed of 2000 r.p.m. p. m. For 20 seconds. This substrate was dried at 180 ° C. for one hour. After that, a rubbing process is performed on this substrate, lines and spaces are formed with a KrF laser having a wavelength of 248 nm, and two substrates are laid so that the rubbing directions are parallel to each other and the portions irradiated with the laser light face each other. The liquid crystal cell having a cell gap of 5 μm was assembled by facing the substrates so that the film was disposed inside. A liquid crystal (LIXON5047L manufactured by Chisso Corporation) is placed in this cell.
C) was implanted and heat treatment was performed at 110 ° C. When the retardation of this cell was measured, it was found that the portion not irradiated with the ultraviolet light had a positive retardation, and the portion irradiated with the laser beam had a negative retardation.

Example 4 A 1: 1 ratio blend material of polyaramid silicone and polyvinyl carbazole was uniaxially stretched, and one size of a portion transmitting ultraviolet rays having a size of 1 mm × 500 μm was formed on a plate made of this polymer. Yes,
The film was irradiated with ultraviolet rays for 10 minutes under a 105 W high-pressure mercury lamp using a mask in which the space between the adjacent transmission portions was blocked by a 500 μm × 500 μm material that did not transmit ultraviolet rays. When the retardation of this plate was measured, it was found that the portion not irradiated with ultraviolet rays had a positive retardation, and the portion irradiated with ultraviolet rays had a negative retardation.

Comparative Example 1 Polyaramide silicone and polyacenaphthylene were dissolved at a ratio of 1: 4 in NMP at 3 wt%, and the solution was applied to a substrate provided with an ITO electrode by a spin coating method. Spin coating was performed at a rotation speed of 2000 r.p.m. p.
m. For 20 seconds. This substrate was dried at 180 ° C. for one hour. Thereafter, the substrate was subjected to a rubbing treatment.
A 5 μm liquid crystal cell was assembled with the two substrates facing each other so that the rubbing directions were parallel to each other so that the films were arranged inside. A liquid crystal (LIXO manufactured by Chisso Corporation) is applied to this cell.
N5047LC), and heat-treated at 110 ° C. When the retardation of this cell was measured, all the retardations were positive.

Claims (9)

[Claims] 1. A phase shifter having optical anisotropy and having a region where the retardation is positive and a region where the retardation is negative. 2. Irradiation of ultraviolet rays or an electron beam to a part of a region of the organic polymer film subjected to the uniaxial treatment causes a region having a positive retardation and a region having a negative retardation on the organic polymer film. 2. The retarder of claim 1, wherein the retarder is formed. 3. A method for producing a retarder, comprising preparing an organic polymer film, performing uniaxial treatment on the organic polymer film, and applying ultraviolet light or an electron beam to a partial region of the organic polymer film. A method comprising the steps of: irradiating to produce a region having a positive retardation and a region having a negative retardation on the organic polymer film. 4. A method for producing a retarder, comprising preparing an organic polymer film, performing uniaxial treatment on the organic polymer film, and irradiating a part of the organic polymer film with ultraviolet light or an electron beam. The liquid crystal is arranged on the organic polymer film, so that the retardation of the liquid crystal arranged in the non-irradiated region has a positive value, and the retardation of the liquid crystal arranged in the irradiated region has a negative value. A method comprising the steps of assembling a liquid crystal element. 5. An organic polymer film, wherein the irradiation of ultraviolet rays or an electron beam results in a negative value of the retardation of the irradiated area. 6. Irradiating a part of the organic polymer film with an ultraviolet ray or an electron beam, the retardation of the liquid crystal disposed in a non-irradiated region on the organic polymer film becomes a positive value, and An organic polymer film, wherein the retardation of a liquid crystal disposed in an irradiated area on the organic polymer film has a negative value. 7. The organic polymer film contains a polymer (A) in which positive retardation is produced by uniaxial treatment and a polymer (B) in which negative retardation is produced by uniaxial treatment and irradiation of ultraviolet rays or electron beams. The organic polymer film according to claim 5. 8. The organic polymer film according to claim 7, wherein at least one kind of the polymer material contained in the polymer (B) is a polymer compound having a cyclic structure having 4 or more carbon atoms. 9. The organic polymer film according to claim 7, wherein the polymer (A) is polyimide, polyamide, polyether, polyester or polyurethane.