JP2001004838A - Manufacture of polarizing diffraction element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for a specular polarizing diffraction element in which diffracted light itself causes specific polarization such as circular polarization and linear polarization. SOLUTION: This manufacturing method comprises a first process in which a cholesteric alignment film having a diffusion rate defined by the ratio of the specular reflection exclusive reflectance (SCE) to the specular reflection inclusive reflectance (SCI) ((SCE/SCI)×100) of less than 15% is formed on an alignment support substrate, a second process in which a diffraction pattern of a diffraction element substrate is transferred to the surface of the cholesteric alignment film, a third process in which the cholesteric alignment film surface and the support substrate 1 are layered through an adhesive layer 1, a fourth process in which the alignment support substrate used in the first process is removed from the cholesteric alignment film, and a fifth process in which the cholesteric alignment film surface from which the alignment support substrate is removed and the support substrate 2 are bonded through an adhesive layer 2.

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 polarized light diffraction element having an excellent design and capable of generating diffracted light having a polarization property.

[0002]

2. Description of the Related Art A diffractive element is a general-purpose optical element that is widely used in the field of spectral optics and the like for the purpose of splitting light and splitting a light beam. Diffraction elements are classified into several types based on their shape.Amplitude type diffraction elements, in which light-transmitting and non-light-transmitting parts are periodically arranged, are phase-type, in which periodic grooves are formed in a highly transparent material. It is usually classified as a diffraction element. Further, they may be classified as a transmission type diffraction element or a reflection type diffraction element according to the direction in which diffracted light is generated.

In the above-described conventional diffraction element, only non-polarized light can be obtained as diffracted light obtained when natural light (non-polarized light) is incident. Polarizing optical instruments such as ellipsometers, which are frequently used in the field of spectroscopy, can only obtain non-polarized light as diffracted light. In general, a method of using diffracted light through a polarizer in order to use only the polarized light component is used.
In this method, there is a problem that about 50% or more of the obtained diffracted light is absorbed by the polarizer, so that the amount of light is reduced by half. For that purpose, it is necessary to prepare a detector having a high sensitivity and a light source having a large amount of light, and the development of a diffraction element in which the diffracted light itself becomes a specific polarized light such as a circularly polarized light or a linearly polarized light has been required.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has succeeded in imparting a diffractive power to a partial region of a cholesteric alignment film by controlling the structure of a liquid crystal layer. More specifically, the present inventors have found a method of easily imparting a new characteristic called diffractive power to a cholesteric alignment film in addition to the selective reflection characteristic and circular polarization characteristic peculiar to a cholesteric liquid crystal, and finally arrived at the present invention.

[0005]

That is, according to the present invention, the ratio of the specular reflection removal reflectance (SCE) to the regular reflection reflectance (SCI) ((SCE / SCI) .times.100) on the alignment support substrate.
A first step of forming a cholesteric alignment film having a diffusivity of less than 15%, a second step of transferring a diffraction pattern of a diffractive element substrate to the surface of the cholesteric alignment film, a cholesteric alignment film surface on which the diffraction pattern is transferred A third step of laminating the substrate and the support substrate 1 with the adhesive layer 1 interposed therebetween, a fourth step of removing the alignment support substrate used in the first step from the cholesteric alignment film, and a cholesteric alignment film surface from which the alignment support substrate has been removed. And a fifth step of laminating the support substrate 2 with the adhesive layer 2 interposed therebetween.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In the first step of the present invention, the diffusivity defined by the ratio ((SCE / SCI) × 100) of the specular reflection removal reflectance (SCE) and the specular reflection reflectance (SCI) on the alignment support substrate is 15%. This is a step of forming a cholesteric alignment film of less than. Here, the regular reflection-inclusive reflectance (SCI) refers to the total reflectance when the object to be measured is uniformly illuminated by diffuse illumination. In addition, the specular reflection removal reflectance (SCE) is obtained by removing a regular reflection light component from a total reflectance when an object to be measured is uniformly illuminated by diffuse illumination (composed of a component of light diffused on the surface of the object to be measured). It refers to diffuse reflectance (total reflectance = specular reflectance + diffuse reflectance). These specular reflection removal reflectance and specular reflection included reflectance can be determined by measuring in accordance with JIS-Z-8722 "Color measurement method-reflection and transmission object". As a specific measuring method, d /
8 (diffuse illumination 8 ゜ light reception) It can be measured using a measuring instrument having an illumination / light receiving optical system, a spectrophotometer CM-3500d manufactured by Minolta.

In the cholesteric alignment film formed on the alignment support substrate in the first step, the diffusivity determined based on the above definition is usually less than 15%, preferably 12% or less, more preferably 10% or less. Spreading rate is 15
%, There is a possibility that a vivid coloration effect with a metallic luster cannot be exhibited.

As a film material for forming the cholesteric alignment film as described above, a high-molecular liquid crystal, a low-molecular liquid crystal, or a mixture thereof can be used. The polymer liquid crystal is not particularly limited as long as the cholesteric alignment can be fixed, and any of a main chain type, a side chain type polymer liquid crystal and the like can be used. Specific examples include main-chain liquid crystal polymers such as polyester, polyamide, polycarbonate, and polyesterimide, and side-chain liquid crystal polymers such as polyacrylate, polymethacrylate, polymalonate, and polysiloxane. Among them, good orientation in forming cholesteric orientation,
A liquid crystalline polyester which is relatively easy to synthesize is desirable. Preferred examples of the constituent units of the polymer include an aromatic or aliphatic diol unit, an aromatic or aliphatic dicarboxylic acid unit, and an aromatic or aliphatic hydroxycarboxylic acid unit.

The low-molecular liquid crystal used as a film material of the cholesteric alignment film is, for example, a compound having a basic skeleton of a biphenyl derivative, a phenylbenzoate derivative, a stilbene derivative into which a functional group such as an acryloyl group, a vinyl group or an epoxy group is introduced. Is mentioned. As the low-molecular liquid crystal, both lyotropic properties and thermotropic properties can be used, but those exhibiting thermotropic properties are more preferable from the viewpoint of workability, process and the like.

In order to improve the heat resistance and the like of the cholesteric alignment film, a crosslinking agent such as a bisazide compound or glycidyl methacrylate may be added to the film material as long as the development of the cholesteric liquid crystal phase is not hindered. By adding a cross-linking agent, cross-linking can be performed in a state where a cholesteric liquid crystal phase is developed. Further, dichroic dyes, dyes, pigments and the like can be appropriately added to the film material as long as the development of the cholesteric liquid crystal phase is not hindered.

As a method for fixing the cholesteric orientation using the film material as described above, a known method, for example, in the case of using a polymer liquid crystal, disposing the polymer liquid crystal on an alignment support substrate, followed by heat treatment or the like A cholesteric liquid crystal phase can be developed, and a cholesteric alignment can be fixed by quenching from that state. When using a low-molecular liquid crystal, after arranging the low-molecular liquid crystal on the alignment support substrate, a cholesteric liquid crystal phase is developed by heat treatment or the like, and cross-linked by light, heat or an electron beam while maintaining that state. A method of fixing the cholesteric orientation or the like can be appropriately adopted.

The cholesteric orientation film has a diffusivity of
A desired diffusion rate can be obtained by appropriately adjusting the heat treatment temperature, the heat treatment time, and the film thickness when forming the cholesteric orientation. The heat treatment temperature, the heat treatment time, and the film thickness cannot be determined unconditionally because they differ depending on the type, composition ratio, various physical properties, and the like of the polymer liquid crystal or the low molecular liquid crystal used as the film material.
0 to 250 ° C, preferably 40 to 200 ° C, particularly preferably 50 to 170 ° C.
Seconds to 2 hours, preferably 10 seconds to 1 hour, particularly preferably 20 seconds to 30 minutes, and the film thickness is usually 0.3 to 30 μm, preferably 0.5 to 20 μm.
m, particularly preferably in the range of 0.7 to 10 μm, a film having a desired diffusivity can be obtained.

Further, examples of the orientation supporting substrate that can be subjected to the first step of the present invention include a glass substrate or a plastic substrate such as a plastic film or a plastic sheet. As the glass substrate, for example, soda glass, silica-coated soda glass, borosilicate glass substrate, or the like can be used. In addition, as a plastic substrate, polymethyl methacrylate, polystyrene, polycarbonate, polyether sulfone,
Substrates such as polyphenylene sulfide, amorphous polyolefin, triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide imide, polyether ether ketone, epoxy resin, and phenol resin can be used. A uniaxial or biaxial stretching operation can be appropriately applied to these alignment support substrates as needed. Further, the substrate may be subjected to a surface treatment such as a hydrophilization treatment, a hydrophobization treatment, and an easy peeling treatment. In addition, as the orientation support substrate, 1
A single type or a laminate of two or more types of substrates can be used as the alignment support substrate.

In the present invention, an alignment support substrate having an alignment film formed thereon is also included in the alignment support substrate. As the alignment film, a rubbed polyimide film is suitably used, but other alignment films known in the art can also be used as appropriate. Also, a plastic substrate or the like obtained by directly imparting an orientation ability by a rubbing treatment without applying polyimide or the like can be used as an orientation support substrate when obtaining a cholesteric orientation film. The method of the alignment treatment is not particularly limited, but any method may be used as long as the liquid crystal molecules are uniformly aligned in parallel with the alignment treatment interface.

Next, as a means for applying the film material on the alignment support substrate, there are melt coating and solution coating, but a solution coating is preferred in the process. In the solution application, a film material is dissolved at a predetermined ratio in a solvent to prepare a solution having a predetermined concentration. As the solvent, although it varies depending on the type of film material to be used, usually, a hydrocarbon system such as toluene, xylene, butylbenzene, tetrahydronaphthalene, and decahydronaphthalene, an ether system such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, and tetrahydrofuran, Methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate,
Butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, ester such as γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, amide such as dimethylacetamide, dichloromethane, carbon tetrachloride, Halogenated hydrocarbons such as tetrachloroethane and chlorobenzene, alcohols such as butyl alcohol, triethylene glycol, diacetone alcohol, and hexylene glycol can be used. If necessary, two or more of these solvents can be used as a mixture. Further, the concentration of the solution cannot be determined unconditionally because it varies depending on the type (composition ratio, etc.) and solubility of the film material used, and furthermore, finally, the film thickness of the target film. Is 3-4
It is appropriately adjusted at 0% by weight.

Further, a surfactant or the like may be added to the solution to facilitate coating. Examples of the surfactant include cationic surfactants such as imidazoline, quaternary ammonium salts, alkylamine oxides, and polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, primary and secondary alcohol ethoxylates. , Alkylphenol ethoxylates, polyethylene glycols and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, etc. Surfactants, amphoteric surfactants such as lauryl amide propyl betaine and lauryl amino acetate betaine, and nonionic surfactants such as polyethylene glycol fatty acid esters and polyoxyethylene alkylamine , Perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl / hydrophilic group-containing oligomer, perfluoroalkyl / lipophilic group-containing oligomer Fluorinated surfactants such as fluoroalkyl group-containing urethanes and the like are included. The amount of the surfactant to be added depends on the type of the surfactant, the solvent, and the supporting substrate to be coated.
The range is 0 ppm to 10%, preferably 50 ppm to 5%, and more preferably 0.01% to 1%.

The film material solution prepared as described above is applied on an alignment support substrate. Examples of the application method include a roll coating method, a die coating method, a bar coating method, a gravure roll coating method, a spray coating method, a dip coating method, and a spin coating method.

After the application, the solvent is removed by drying, and after the coating film of the film material formed on the alignment supporting substrate is subjected to the cholesteric alignment under the heat treatment conditions described above,
By fixing the orientation, a cholesteric orientation film having a desired diffusivity can be formed on the substrate. As a method of fixing the cholesteric alignment, when a film material mainly composed of a polymer liquid crystal is used, a cholesteric alignment film in which the cholesteric alignment is fixed can be obtained by rapidly cooling to a temperature below the glass transition point. . When a film material mainly composed of low-molecular liquid crystal is used, the cholesteric alignment is formed in the liquid crystal state, and then the low-molecular liquid crystal is cross-linked by irradiating an electron beam, ultraviolet light, visible light or infrared light (heat ray). As a result, a cholesteric alignment film in which the cholesteric alignment is fixed can be obtained.

As the optical parameter of the cholesteric alignment film formed on the alignment support substrate, the number of spiral windings in the cholesteric alignment is usually from 2 to 10 turns, preferably from 2 to 6 turns. If the number of spiral turns is less than 2 turns,
If the number of windings is more than 10 turns, the effect as a polarization diffraction element may not be exhibited. Further, as the wavelength band of cholesteric selective reflection in the film,
Usually, it is preferably 30 to 150 nm, and the center wavelength of the cholesteric selective reflection is usually 380 to 780 n.
m, preferably in the visible range from 420 to 700 nm, or 8
It is desirably in the near infrared range of 00 to 2000 nm, preferably 850 to 1100. When the center wavelength of the cholesteric selective reflection is out of the above range when using the polarization diffraction element of the present invention in the visible region, there is a possibility that the reflected color becomes faint and lacks vividness. When the element is used in the near-infrared region, cholesteric selective reflection is used using an appropriate light source and / or detector. However, if the center wavelength is out of the above range, the amount of light is insufficient with a general-purpose light source. Or, a general-purpose detector may cause insufficient sensitivity.

The second step of the present invention is a step of transferring the diffraction pattern of the diffraction element substrate to the surface of the cholesteric alignment film obtained in the first step. The material of the diffraction element substrate used when transferring the diffraction pattern to the cholesteric alignment film may be a material such as a metal or a resin, or a material having a diffraction function on the film surface, or a diffraction function on the film. Any material may be used as long as it has a diffraction function, such as a thin film having a thin film transferred thereon. Above all, in view of ease of handling and mass productivity, a film or a film laminate having a diffraction function is more desirable.

The term "diffraction element" as used herein includes, as its definition, any diffraction element that generates diffracted light, such as an original flat hologram. The type may be a diffraction element derived from the surface shape, a so-called film thickness modulation hologram type, or a phase element independent of the surface shape or a surface shape converted into a refractive index distribution, a so-called refraction. A rate modulation hologram type may be used. In the present invention, the type of the film thickness modulation hologram is more preferably used because the diffraction pattern information of the diffraction element can be more easily given to the liquid crystal. In addition, any type of refractive index modulation can be suitably used in the present invention as long as it has undulations that cause diffraction in the surface shape. The grating interval of the diffraction pattern on the diffraction element substrate is not particularly limited, but is usually 0.56 μm to 6.3.
0 μm, preferably 0.59 μm to 3.20 μm, more preferably 0.72 μm to 2.10 μm is desirable when the polarization diffraction element of the present invention is practically used.

The conditions for transferring the diffraction pattern to the cholesteric alignment film cannot be unequivocally determined because it varies depending on the physical properties of the cholesteric alignment film, the material of the diffraction element substrate, and the like. Can be carried out under heating and / or pressurizing conditions of 70 to 180 ° C. and a pressure of 0.05 to 80 MPa, preferably 0.1 to 20 MPa. If the temperature is below 40 ° C,
In a cholesteric alignment film having a sufficiently stable alignment state at room temperature, the transfer of the diffraction pattern may be insufficient. If the temperature exceeds 300 ° C., the cholesteric alignment film may be decomposed or deteriorated. If the pressure is lower than 0.05 MPa, the transfer of the diffraction pattern may be insufficient. If the pressure is higher than 80 MPa, the cholesteric alignment film and other substrates may be broken, which is not desirable.

The time required for the transfer differs depending on the type of the film material forming the cholesteric alignment film, the film form, the diffraction pattern type, the material of the diffraction element substrate, and the like. Seconds or more, preferably 0.05 seconds to 1 minute. If the processing time is shorter than 0.01 second, the transfer of the diffraction pattern may be insufficient. A processing time exceeding 1 minute is not desirable from the viewpoint of productivity.

As a specific method of transferring the diffraction pattern to the cholesteric alignment film, for example, a general compression molding machine, a rolling mill, a calender roller, a heat roller, a laminator, a hot stamp, an electric heating plate, a thermal plate, which satisfies the above-mentioned conditions. The diffraction pattern of the diffraction element substrate can be transferred to the cholesteric alignment film by using a head or the like with a molding machine or the like in a state where the liquid crystal surface of the cholesteric alignment film is in contact with the diffraction pattern surface. Further, the transfer of the diffraction pattern is not limited to only one side of the cholesteric alignment film, and the diffraction pattern can be transferred to both sides of the cholesteric alignment film by the same method.

After the diffraction pattern of the diffraction element substrate is transferred to the cholesteric alignment film by the method and under the conditions described above, the diffraction element substrate is peeled off from the cholesteric alignment film. The cholesteric alignment film from which the diffraction element substrate has been removed has a region exhibiting diffractive ability on the surface of the film on which the diffraction pattern has been transferred. Here, the region exhibiting the diffractive power means a region which produces an effect such that the light transmitted through the region or the light reflected by the region wraps around a portion which is geometrically shadow. The presence or absence of a region having a diffractive ability is confirmed by, for example, the presence or absence of light (higher-order light) emitted at a certain angle other than light (0th-order light) that enters a laser beam or the like into the above-mentioned region and transmits or reflects linearly. can do. Alternatively, by observing the surface shape or cross-sectional shape of the liquid crystal layer with an atomic force microscope, a transmission electron microscope, or the like, it can be confirmed whether or not a region having a diffractive ability is formed. The regions exhibiting diffractive power can also be formed on a plurality of regions of the cholesteric alignment film, for example, on each of the front and back surfaces of the film. Further, the region exhibiting diffractive power does not necessarily need to be formed as a layer having a uniform thickness on the film surface, for example, and the region exhibiting diffractive power is formed on at least a part of the film surface. For example, the effect as a polarization diffraction element can be exhibited. Further, the region exhibiting the diffractive power can be formed so as to model a desired figure, pictogram, numeral or the like. Further, when there are a plurality of regions exhibiting the diffractive power, it is not necessary that all the regions exhibit the same diffractive power, and the respective regions may exhibit different diffractive powers.

When the region exhibiting diffractive power is formed in a layer state, the thickness of the layer (region) exhibiting diffractive power is usually 5 times the film thickness of the cholesteric alignment film.
0% or less, preferably 30% or less, more preferably 1% or less.
It is desirable that the layer is formed in a layer state having a thickness of 0% or less. If the thickness of the layer (region) exhibiting a diffractive ability exceeds 50%, effects such as selective reflection characteristics and circular polarization characteristics due to the cholesteric liquid crystal phase are reduced, and the effect as a polarization diffraction element may not be obtained. There is.

Further, in the second step of the present invention, the cholesteric alignment film on which the diffraction pattern of the diffraction element substrate has been transferred has an alignment state on the surface of the film on which the diffraction pattern has been transferred, that is, an alignment state of a region exhibiting diffractive ability. A cholesteric orientation in which the helical axis orientation is not uniformly parallel to the film thickness direction, preferably the helical axis direction is not uniformly parallel to the film thickness direction, and the helical pitch is not evenly spaced in the film thickness direction It is desirable to form a cholesteric orientation. In other regions, a helical structure in which the helical axis orientation is uniformly parallel to the film thickness direction and the helical pitch is uniformly spaced uniformly in the film thickness direction is the same as the normal cholesteric orientation. It is desirable to form.

In the cholesteric oriented film of the present invention, when a region having a diffractive power is present on one film surface region, the film surface having the diffractive power is opposite to the film surface having the diffractive power. It shows an optical effect, a coloring effect and the like slightly different from those of the surface. Therefore, it is desirable to select the arrangement position of the film surface of the cholesteric alignment film according to the use and the intended function.

The diffraction angle of the cholesteric alignment film in the region showing the diffractive power is not particularly limited, but the diffraction angle of the first-order diffracted light is usually 5 ° to 80 °,
Preferably it is in the range of 10 ° to 70 °, more preferably 15 ° to 60 °. If the diffraction angle is smaller than 5 °,
The effect due to diffraction may not be confirmed. Further, when the diffraction angle is larger than 80 °, there is a possibility that inconvenience may occur when the diffraction effect is used for a design purpose such that the diffraction effect cannot be confirmed unless observed from almost right beside the film.

The third step of the present invention is a step of laminating, via the adhesive layer 1, the diffraction pattern transfer surface of the cholesteric alignment film after the transfer of the diffraction pattern obtained in the second step and the support substrate 1. The support substrate 1 used in the third step is not particularly limited as long as it is a substrate having a shape such as a sheet, a film, or a plate and having self-supporting properties. If the support substrate 1 needs to be removed in a sixth step described later, the shape,
It is necessary to have removability together with self-supporting property. As such a supporting substrate 1, a plastic film having a releasable property can be desirably used. Here, the term “removability” means that, in a state where the cholesteric alignment film and the support substrate 1 are bonded via an adhesive, the film can be separated at the interface between the adhesive and the support substrate 1, and is preferably supported via the adhesive. It is desirable that, after the air side surface of the cholesteric alignment film transferred to the substrate 1 and the support substrate 2 described below are bonded to each other via an adhesive and then the support substrate 1 can be peeled off at the interface with the adhesive directly contacted. As the support substrate 1 as described above used in the third step of the present invention, the peel strength at the interface with the adhesive (after curing) (180 ° peel test, peel speed 30
cm / min), usually 0.5 to 80 gf / 25 m
m, preferably those having a peel strength of 2 to 50 gf / 25 mm. Specific examples of a plastic film suitable for the support substrate 1 include olefin resins such as polyethylene, polypropylene, and 4-methylpentene-1 resin, polyamide, polyimide, polyamideimide, polyetherimide, and polyetherketone. Polyether ether ketone, polyether sulfone, polyketone sulfide, polysulfone, polystyrene, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyacetal,
Examples thereof include polycarbonate, polyvinyl alcohol, and cellulosic plastics. These plastic films may be used by themselves, or those coated with a silicone coat, an organic thin film or an inorganic thin film, or chemically treated to impart appropriate removability. And those subjected to physical processing can be used. As the supporting substrate 1 used in the third step of the present invention, a plastic film obtained by treating polypropylene, polyetheretherketone, polyethylene terephthalate, polycarbonate or the like or a film surface of these films with a release agent such as silicone is used as an adhesive. It is desirable because it has both proper adhesiveness and peelability.

The adhesive layer 1 interposed between the cholesteric alignment film and the supporting substrate 1 is not particularly limited, and various conventionally known adhesives and adhesives, for example, light or electron beam curable adhesives can be used. A reactive adhesive, a hot-melt adhesive or the like can be used as appropriate.

As the reactive adhesive, a prepolymer and / or a monomer having photo- or electron beam polymerizability, if necessary, other monofunctional or polyfunctional monomers, various polymers, a stabilizer, a photopolymerization initiator, What mixed a sensitizer etc. can be used.

Examples of the prepolymer having photo- or electron beam polymerizability include polyester acrylate, polyester methacrylate, polyurethane acrylate, polyurethane methacrylate, epoxy acrylate, epoxy methacrylate, polyol acrylate, and polyol methacrylate. . Examples of the monomer having photo- or electron beam polymerizability include monofunctional acrylate, monofunctional methacrylate, difunctional acrylate, difunctional methacrylate, trifunctional or higher polyfunctional acrylate, and polyfunctional methacrylate. These can also use a commercial item, for example, Aronix (acrylic special monomer, oligomer;
Toagosei Co., Ltd.), Light Ester (Kyoeisha Chemical Co., Ltd.),
Viscote (manufactured by Osaka Organic Chemical Industry) or the like can be used.

As the photopolymerization initiator, for example, benzophenone derivatives, acetophenone derivatives, benzoin derivatives, thioxanthones, Michler's ketone, benzyl derivatives, triazine derivatives, acylphosphine oxides, azo compounds and the like can be used. .

The viscosity of the reactive adhesive of the light or electron beam curing type is appropriately selected depending on the processing temperature of the adhesive and the like, and cannot be specified unconditionally.
Pa · s, preferably 50 to 1000 mPa · s, more preferably 100 to 500 mPa · s. Viscosity 1
When it is lower than 0 mPa · s, it becomes difficult to obtain a desired thickness. On the other hand, if it is higher than 2000 mPa · s, the workability may decrease, which is not desirable. When the viscosity is out of the above range, it is preferable to appropriately adjust the solvent and the monomer ratio to obtain a desired viscosity.

When a photocurable reactive adhesive is used, a known curing method such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, or a xenon lamp is used as a method for curing the adhesive. be able to. Although the exposure amount cannot be determined unconditionally because it differs depending on the type of the reactive adhesive used, it is usually 50 to 2000 mJ.
/ Cm ² , preferably 100 to 1000 mJ / cm ² .

When an electron beam-curable reactive adhesive is used, the method of curing the adhesive is appropriately selected depending on the penetrating power and the curing power of the electron beam, and cannot be determined unconditionally. Usually, curing can be carried out by irradiating under an acceleration voltage of 50 to 1000 kV, preferably 100 to 500 kV.

When a hot melt adhesive is used as the adhesive, the adhesive is not particularly limited, but the operating temperature of the hot melt is 80 to 200 ° C., preferably 100 to 200 ° C.
Those having a temperature of about 160 ° C. are desirably used from the viewpoint of workability and the like. Specifically, for example, polyvinyl acetal resins such as ethylene-vinyl acetate copolymer resins, polyester resins, polyurethane resins, polyamide resins, thermoplastic rubbers, polyacrylic resins, polyvinyl alcohol resins, and polyvinyl butyral , Petroleum resin,
Examples include those manufactured using a terpene resin, a rosin resin, or the like as a base resin.

The use of a pressure-sensitive adhesive as an adhesive is not particularly limited. For example, a rubber-based, acrylic, silicone-, or polyvinyl ether-based pressure-sensitive adhesive can be used. Since the thickness of the adhesive varies depending on the application used and its workability, etc., it cannot be said unconditionally,
Usually, it is 0.5 to 50 μm, preferably 1 to 10 μm.

The method of forming the adhesive is not particularly limited, and examples thereof include a roll coating method, a die coating method, a bar coating method, a curtain coating method, an extrusion coating method, a gravure roll coating method, and a spray coating method. A known method such as a spin coating method or a spin coating method can be used to form the film on the support substrate or on the film surface to which the diffraction pattern of the cholesteric alignment film has been transferred, or on both the support substrate 1 and the cholesteric alignment film.

The adhesive layer 1 used in the third step may contain an ultraviolet ray inhibitor and a hard coat agent. The ultraviolet absorber is not particularly limited as long as it is compatible or dispersible with the adhesive component as described above. For example, a benzophenone compound, a salicylate compound, a benzotriazole compound, an oxalic acid anilide compound, a cyanoacrylate compound Organic UV absorbers such as compounds and inorganic UV absorbers such as cesium oxide, titanium oxide and zinc oxide can be used. Among them, a benzophenone-based compound having high ultraviolet absorption efficiency is preferably used. In addition, one or more ultraviolet absorbers can be added. The hard coating agent is not particularly limited as long as it is compatible or dispersible with the adhesive component. For example, organopolysiloxanes, photocurable resin-based acrylic oligomers, urethane acrylates, epoxy acrylates, polyesters An acrylate-based, thermosetting resin-based acryl-silicon-based, or inorganic compound such as ceramics can be used. Among them, organopolysiloxane-based and photo-curable resin-based acrylic oligomer-based hard coat agents are preferably used.

The mixing ratio of the ultraviolet absorber and / or the hard coat agent in the adhesive layer 1 used in the third step depends on the adhesive component used, but is usually 0.1%.
-20% by weight, preferably 0.5-10% by weight.
Further, an adhesive layer 1 used for bonding the cholesteric alignment film used in the third step to the support substrate 1
Some of these include light stabilizers such as hindered amines and quenchers, antistatic agents, slipperiness improvers, dyes, pigments, surfactants, fine silica and zirconia in addition to ultraviolet absorbers and hard coat agents. And various additives such as fillers. The mixing ratio of these various additives is
There is no particular limitation as long as the effects of the present invention are not impaired, but usually 0.01 to 10% by weight, preferably 0.05 to 10% by weight.
5% by weight.

In the third step, the method of laminating the film surface on which the diffraction pattern of the cholesteric alignment film is transferred and the supporting substrate 1 via the adhesive layer 1 is not particularly limited. The pattern can be laminated by appropriately selecting from various devices exemplified as a method of transferring the pattern to the cholesteric alignment film.

Next, the alignment support substrate / cholesteric alignment film / adhesive layer 1 obtained in the previous steps
As a fourth step, a step of removing the alignment support substrate used in the first step from the laminate formed in the order of / support substrate 1 is performed.

The method of removing the alignment supporting substrate from the cholesteric alignment film is not particularly limited, and examples thereof include a method of removing the alignment supporting substrate and a method of dissolving the alignment supporting substrate.
As a peeling removal method, for example, a method of applying an adhesive tape to a corner end of the orientation support substrate and artificially peeling,
A method of mechanically peeling using a roll or the like, a method of mechanically peeling after dipping in a poor solvent for all structural materials,
A method of peeling by applying ultrasonic waves in a poor solvent, a method of peeling by giving a temperature change by using a difference in thermal expansion coefficient between the alignment support substrate and the cholesteric alignment film, the alignment support substrate itself, or on the alignment support substrate And a method of dissolving and removing the alignment film. The releasability differs depending on various physical properties of the film material forming the cholesteric alignment film and the adhesion to the alignment support substrate, and therefore, a method most suitable for the system should be adopted.

In the present invention, after the orientation supporting substrate is removed in the fourth step, the step of laminating the cholesteric orientation film surface from which the orientation supporting substrate has been removed and the supporting substrate 2 via the adhesive layer 2 as a fifth step. Do. The support substrate 2 used in the fifth step is not particularly limited as long as it has a shape such as a sheet, a film, and a plate. For example, polyimide, polyamideimide, polyamide, or polyether Imide, polyether ether ketone, polyether ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyvinyl chloride, polystyrene, polypropylene,
Polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl alcohol, polyacetal, polyarylate, cellulosic plastics, epoxy resin, phenolic resin sheet, film or substrate, paper, synthetic paper, etc. Paper, metal foil, glass plate and the like can be appropriately selected and used.
In addition, the support substrate 2 may have a surface with irregularities.

The adhesive layer 2 interposed between the cholesteric alignment film and the support substrate 2 is not particularly limited, and various conventionally known adhesive layers described as the adhesive layer 1 in the third step are used. Adhesives, for example, a light or electron beam-curable reactive adhesive, a hot-melt adhesive, and the like are used as appropriate, for example, a roll coating method, a die coating method, a bar coating method, a curtain coating method, an extrusion coating method, and a gravure roll. Using a known method such as a coating method, a spray coating method, or a spin coating method, the supporting substrate 2
Alternatively, it can be formed on the cholesteric alignment film surface from which the alignment support substrate has been removed, or on both the support substrate 2 and the cholesteric alignment film surface.

According to the present invention, the first to fifth steps described above are performed.
Through the steps, a polarization diffraction element configured in the order of support substrate 2 / adhesive layer 2 / cholesteric alignment film / adhesive layer 1 / support substrate 1 can be manufactured. Here, when the support substrate 1 used in the third step is not optically transparent, the effect as the support substrate 1 or the polarization diffraction element exhibiting undesired optical characteristics in the intended use is lost. When the support substrate 1 or the like is used, or when a substrate having removability is used as the support substrate 1, the support substrate 1 used in the third step is removed from the cholesteric alignment film as a sixth step. It is possible to manufacture a polarization diffraction element configured in the order of substrate 2 / adhesive layer 2 / cholesteric alignment film / adhesive layer 1. Here, in the third step, a function as a protective layer can be imparted to the adhesive layer 1 by blending an ultraviolet absorber and / or a hard coat agent in the adhesive layer 1.

The method of removing the support substrate 1 in the sixth step is, for example, a method of removing only the support substrate 1 or dissolving the support substrate 1 in the same manner as the method of removing the oriented support substrate in the fourth step. And the like. Examples of the peeling and removing method include a method of applying an adhesive tape to a corner end of the support substrate 1 to artificially peel it, a method of mechanically peeling using a roll or the like, and a method of dipping in a poor solvent for all structural materials. A method of mechanically peeling, a method of peeling by applying an ultrasonic wave in a poor solvent, a method of peeling by giving a temperature change using a difference in thermal expansion coefficient between the support substrate 1 and the adhesive layer 1, a method of peeling the support substrate A method of dissolving and removing 1 itself can be exemplified. Since the releasability depends on various physical properties of the adhesive layer 1 and the adhesion to the support substrate 1, a method most suitable for the system should be adopted.

Further, in the present invention, even if the ultraviolet absorbent and / or the hard coat agent is not blended in the adhesive layer 1 in the third step, or if it is blended,
Providing a protective layer as a seventh step on the surface of the cholesteric alignment film from which the substrate 1 has been removed for the purpose of further protecting the surface of the cholesteric alignment film after peeling and removing the support substrate 1, increasing strength, and improving environmental reliability. Can be. The protective layer is not particularly limited as long as it has an ultraviolet absorbing property and / or a hard coat property. For example, a material in which a protective layer-forming material containing an ultraviolet absorber and a hard coat agent is formed into a film, a sheet, a thin film, or a plate. Further, a protective layer having an ultraviolet absorbing property made of a protective layer forming material containing an ultraviolet absorbent (hereinafter, referred to as an ultraviolet absorbing layer) and a protective layer having a hard coating property made of a protective layer forming material containing a hard coat agent (Hereinafter, a hard coat layer) may be used as the protective layer in the present invention. In addition, a laminate of a commercially available ultraviolet cut film and a hard coat film can be used as the protective layer. A laminate formed by applying various hard coat agents to the ultraviolet absorbing layer to form a film can also be used as the protective layer.
Here, each of the ultraviolet absorbing layer and the hard coat layer may be formed of two or more layers, and each layer can be laminated via an adhesive layer or the like.

As the material for forming the protective layer, those having high light transmittance are desirable. For example, polyethylene, polypropylene, poly (4-methyl-pentene-1), polystyrene, ionomer, polyvinyl chloride, polymethyl methacrylate, polyethylene terephthalate, polyamide,
A material obtained by adding an ultraviolet absorber and / or a hard coat agent to polysulfone, a cellulose resin, or the like can be used. Further, as the protective layer, an adhesive composition obtained by adding an ultraviolet absorber and / or a hard coat agent to a heat, light or electron beam curing type reactive adhesive can be used, and a cured product of the adhesive composition can be used. Can be used as a protective layer.

The ultraviolet absorber is not particularly limited as long as it is compatible or dispersible in the protective layer forming material. Examples thereof include benzophenone compounds, salicylate compounds, and the like.
Organic ultraviolet absorbers such as benzotriazole-based compounds, oxalic anilide-based compounds, and cyanoacrylate-based compounds, and inorganic ultraviolet absorbers such as cesium oxide, titanium oxide, and zinc oxide can be used. Among them, a benzophenone-based compound having high ultraviolet absorption efficiency is preferably used. In addition, one or more ultraviolet absorbers can be added. The blending ratio of the ultraviolet absorber in the protective layer varies depending on the material for forming the protective layer to be used.
It is 1 to 20% by weight, preferably 0.5 to 10% by weight.

The hard coating agent is not particularly limited as long as it is compatible or dispersible in the protective layer forming material.
For example, use of an inorganic compound such as an organopolysiloxane-based, photo-curable resin-based acrylic oligomer-based, urethane acrylate-based, epoxy acrylate-based, polyester acrylate-based, thermosetting resin-based acryl-silicone-based, or ceramics. Can be. Above all, an organopolysiloxane-based or photo-curable resin-based acrylic oligomer-based hard coat agent is preferably used from the viewpoint of film-forming properties and the like. These hard coat agents are
Either a solventless type or a solvent type can be used.

The material for forming the protective layer includes, in addition to an ultraviolet absorber and a hard coat agent, if necessary, a light stabilizer such as a hindered amine or a quencher, an antistatic agent, a slipperiness improver, a dye, a pigment, a surfactant. Various additives such as fillers such as fine silica and zirconia can also be blended. The mixing ratio of these various additives is not particularly limited as long as the effects of the present invention are not impaired, but is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight.

Further, the ultraviolet absorbing layer constituting the protective layer can be formed using a material obtained by appropriately blending an ultraviolet absorbing agent and, if necessary, a light stabilizer into the above-described protective layer forming material. Further, a commercially available ultraviolet cut film or the like can be used as the ultraviolet absorbing layer in the present invention.

The hard coat layer constituting the protective layer is
The protective layer can be formed by using a material in which a hard coat agent and various additives are added to the protective layer forming material described above. The hard coat layer may be formed by applying the above hard coat agent on a transparent support film. As a transparent support film, polymethyl methacrylate, polystyrene, polycarbonate,
Examples include films formed from polyether sulfone, amorphous polyolefin, triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, and the like.

The ultraviolet absorbing layer and the hard coat layer are laminated via an adhesive or the like, and can be used as the protective layer in the present invention. As the adhesive, a heat, light or electron beam curable reactive adhesive or the like can be used. The protective layer can also be formed by using an adhesive containing an ultraviolet absorber and laminating a separately prepared hard coat layer on the cholesteric alignment film. Further, a dye, a pigment, a surfactant and the like may be appropriately added to the adhesive as needed.

Further, as the hard coat layer, a vehicle resin for gravure ink or the like can be preferably used.
Examples of the gravure ink vehicle resin include nitrocellulose, ethyl cellulose, polyamide resin, vinyl chloride, chlorinated polyolefin, acrylic resin, polyurethane, polyester, and the like. In addition, hard resins such as ester gum, dammar gum, maleic resin, alkyd resin, phenol resin, ketone resin, xylene resin, terpene resin, petroleum resin, etc. are used in the gravure ink vehicle resin in order to improve adhesion and film strength. May be blended.

The structure of the hard coat layer may be a single hard coat layer or a composite layer according to the required weather resistance and the like. As the composite layer, for example, a hard coat layer containing an organopolysiloxane, a hard coat layer containing a photocurable resin, a hard coat layer containing a thermosetting resin,
A composite layer composed of two or more layers, such as a hard coat layer containing an inorganic compound, may be used as the hard coat layer.

Further, the degree of the hard coat property, that is, the hardness cannot be determined unconditionally depending on the material constituting the polarization diffraction element. However, when the evaluation is carried out according to the test method described in JIS L0849, at least the criteria for judging discoloration are as follows. It is desirable that the number be 3 or more, preferably 4 or more.

The protective layer formed on the cholesteric alignment film surface from which the alignment supporting substrate has been removed, and the ultraviolet absorbing layer and the hard coat layer constituting the protective layer are generally formed by a roll coating method, a dipping method, a gravure coating method, or the like. ,
Known methods such as a bar coating method, a spin coating method, a spray coating method, and a printing method can be employed. After forming a film on the cholesteric alignment film or the support film by these methods, the protective layer can be formed by performing a post-treatment according to the protective layer forming material used. Examples of a method for forming a protective layer composed of a composite layer of an ultraviolet absorbing layer and a hard coat layer include a method of directly applying and forming a hard coating agent on the ultraviolet absorbing layer, a method of laminating via an adhesive or the like, and the like. .

The thickness of the protective layer cannot be specified unconditionally because it differs depending on the required performance of the ultraviolet absorbing property and the hard coating property, but it is usually 0.1 to 100 μm, preferably 1 to 50 μm. Also, when the protective layer is formed of a composite layer with an ultraviolet absorbing layer and a hard coat layer, the total thickness of each layer is preferably within the above range.

The polarization diffraction element of the present invention obtained as described above has a unique effect that the diffracted light has a circular polarization property, which is not possible with the conventional optical member. Due to this effect, it is possible to extremely increase the light use efficiency by using, for example, a spectroscopic optical device that requires polarized light, such as an ellipsometer. Conventional spectroscopic optical devices that require polarized light use a diffraction element such as a diffraction grating or prism to separate the light emitted from the light source for each wavelength and then transmit the light through the polarizer, or transmit the light through the polarizer and then separate the light. It was necessary to have a polarizer. This polarizer has a problem that it absorbs about 50% of the incident light and has a problem of extremely low light utilization efficiency due to reflection at the interface. However, the polarizer obtained by the manufacturing method of the present invention has a problem. By using the diffraction element, the light use efficiency is extremely high, and it is theoretically possible to use about 100%. Further, the polarization diffraction element obtained by the production method of the present invention can easily control transmission and blocking of diffracted light by using a normal polarizing plate. Normally, diffracted light having no polarization cannot be completely blocked by any combination of polarizing plates. That is, in the polarization diffraction element obtained by the production method of the present invention, for example, right-polarized diffracted light can be completely blocked only when a left circularly polarizing plate is used, and even when other polarizing plates are used. Complete interruption cannot be achieved. Because of such an effect, for example, in an environment in which an observer observes a diffraction image through a polarizing plate, by changing the state of the polarizing plate, the diffraction image suddenly emerges from the dark field, or suddenly disappears. It becomes possible.

As described above, the polarization diffraction element obtained by the manufacturing method of the present invention has a very wide range of applications as a new diffraction function element, and various optical elements, optoelectronic elements, decorative members, and forgery prevention elements. And so on.

Specific examples of the optical element and the optoelectronic element include a transparent and isotropic film, for example, a triacetyl cellulose film such as Fujitac (manufactured by Fuji Photo Film Co., Ltd.) and Konikatac (manufactured by Konica Corporation), and a TPX film. (Manufactured by Mitsui Chemicals, Inc.), Arton film (manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX film (manufactured by Nippon Zeon), acrylene film (manufactured by Mitsubishi Rayon), etc.
By obtaining a polarization diffraction element as the support substrate 2 in the process, it is possible to develop the optical element for various optical uses. For example, the polarization diffraction element is TN (twisted).
nematic) -LCD (Liquid Crystal)
al Display), STN (Super Twi)
Sted Nematic-LCD, ECB (Ele)
critically Controlled Wire
fringence) -LCD, OMI (Optica)
l Mode Interference) -LCD,
OCB (Optically Compensated)
Birefringence) -LCD, HAN (H
ybrid Aligned Nematic) -LC
D, IPS (In Plane Switching)
By providing a liquid crystal display such as an LCD, various LCDs with improved color compensation and / or improved viewing angle can be obtained. Further, a spectroscopic optical device that requires the polarized light to be polarized as described above, a polarizing optical element that obtains a specific wavelength by a diffraction phenomenon, an optical filter,
It can also be used as a circularly polarizing plate, light diffusing plate, etc.
Further, it is possible to provide various optical members capable of exhibiting an optical effect that has not existed conventionally as an optical element or an optoelectronic element, for example, a linear polarizing plate can be obtained by combining with a quarter wavelength plate.

As the decorative member, various design molding materials can be obtained, including a new design film having a combination of iridescent coloring effect by diffractive ability and colorful coloring effect by cholesteric liquid crystal. In addition, since it can be made into a thin film, it can be expected to greatly contribute to differentiation from other similar products by a method of attaching it to an existing product or the like or integrating it. For example, by attaching a polarization diffraction element incorporating a designable diffraction pattern to a glass window or the like, or by using a glass window or the like as the support substrate 1 in the third step or the support substrate 2 in the fifth step, externally, Depending on the viewing angle, the selective reflection peculiar to the cholesteric liquid crystal accompanied by the diffraction pattern looks different colors, and the fashionability is excellent. In addition, it is possible to provide a window in which the inside is hardly seen from the bright outside, and the outside is excellent in the interior from the inside.

The anti-counterfeit element can be used as a new anti-counterfeit film, seal, label or the like having both the anti-counterfeit effect of the diffraction element and the cholesteric liquid crystal. Specifically, as the support substrate 1 in the third step or the support substrate 2 in the fifth step of the present invention, a car driver's license, an identification card, a passport, a credit card, a prepaid card, various cash vouchers, a gift card, and securities By using such a card substrate, mount, or the like, the polarization diffraction element can be integrated with or partially provided with the card substrate, mount, or the like, specifically, attached, embedded, or woven into paper. Further, the polarizing diffraction element obtained by the production method of the present invention has a region exhibiting diffraction ability in the surface region of the cholesteric alignment film, and the film surface is covered with an adhesive layer, and further has a wavelength of the cholesteric liquid crystal. Selective reflectivity, circularly polarized light selective reflectivity, viewing angle dependence of color, and the effect of exhibiting a beautiful cholesteric color are also provided. Therefore, when the polarizing diffraction element obtained by the production method of the present invention is used as an anti-counterfeiting element, it is difficult to forge the polarizing diffraction element, and more specifically, a region exhibiting diffractive ability is formed on the film surface. It can be said that it is extremely difficult to forge a cholesteric alignment film. In addition to the anti-counterfeiting effect, it also has an iridescent color effect of the diffraction element and a vivid color effect of the cholesteric liquid crystal with a metallic luster, and thus has excellent design properties. For these reasons, the polarization diffraction element obtained by the production method of the present invention is very suitable as a forgery prevention element.

These applications are only examples, and the polarizing diffraction element obtained by the manufacturing method of the present invention is not limited to various applications in which a single diffraction element or a single cholesteric alignment film in which ordinary cholesteric alignment is fixed is used. In addition, since it is possible to exhibit a new optical effect, it can be applied to various uses other than the above-mentioned uses.

[0069]

EXAMPLES Examples will be described below, but the present invention is not limited to these examples.

(Example 1) 50 mmol of terephthalic acid,
Hydroxybenzoic acid 20 mmol, catechol 20 mm
ol, (R) -2-methyl-1,4-butanediol 1
0 mmol and 100 mg of sodium acetate in a nitrogen atmosphere at 180 ° C. for 1 hour, 200 ° C. for 1 hour,
The polycondensation reaction was performed while the temperature was raised stepwise at 50 ° C. for 1 hour.

Next, the polycondensation reaction was continued at 250 ° C. for 2 hours while flowing nitrogen, and the polycondensation was further performed at the same temperature under reduced pressure for 1 hour. After dissolving the obtained polymer in tetrachloroethane, reprecipitation was performed with methanol to obtain a liquid crystalline polyester.

A solution of the obtained liquid crystalline polyester in N-methyl-2-pyrrolidone (20% by weight) was prepared, and the solution was rubbed with polyphenylene sulfide (PP).
S) It was applied on a film by a spin coating method. After the application, a drying treatment was performed to remove N-methyl-2-pyrrolidone, and a liquid crystalline polyester coating film was formed on the PPS film. The film thickness after drying measured by a stylus-type film thickness meter was about 1.6 μm.

Next, a liquid crystalline polyester coating film was
A heat treatment was performed for 5 minutes in a heating atmosphere at 5 ° C., and the mixture was cooled to room temperature to obtain a liquid crystalline polyester film exhibiting a bright golden reflection color on the PPS film.

When the transmission spectrum of the film was measured with an ultraviolet-visible-near-infrared spectrophotometer V-570 manufactured by JASCO Corporation, a cholesteric orientation showing a selective reflection having a center wavelength of 600 nm and a selective reflection wavelength bandwidth of about 110 nm was obtained. Was confirmed to be a fixed cholesteric alignment film. Then, the specular colorimeter CM-3500d manufactured by Minolta Co., Ltd. was used to measure the specular reflection removal reflectance (SCE) and the specular reflectance (SCI) of the obtained film. The measured values were 4% for SCE and 45% for SCI. The diffusivity was about 9%.

Next, a ruled-line diffraction grating film manufactured by Edmund Scientific Japan (900 / m
m) The liquid crystal surface of the cholesteric alignment film was placed so that the diffraction surface of the cholesteric alignment film was facing each other, placed on a plate of a 26-ton press manufactured by Shinei Sangyo Co., Ltd., and heated and pressed at 90 ° C. and 5 MPa for 1 minute. It was taken out and the scored type diffraction grating film was removed.

Next, a commercially available photocurable acrylic adhesive was applied to the cholesteric alignment film surface from which the diffraction grating film had been removed to a thickness of 5 μm using a bar coater.
After applying a triacetyl cellulose (TAC) film to the coating surface using a laminator and curing the adhesive by ultraviolet irradiation, PPS used as an alignment support substrate
The film was peeled off in the direction of 180 °.

Apply the photocurable acrylic adhesive to the cholesteric alignment film surface from which the PPS film has been removed.
μm, a TAC film was adhered to the application surface using a laminator, and the adhesive was cured by ultraviolet irradiation to obtain a laminate.

In the obtained laminate, the iridescent color caused by the diffraction pattern and the selective reflection peculiar to the cholesteric liquid crystal were clearly recognized. When the alignment state of the cholesteric alignment film was observed by a polarizing microscope and a transmission electron microscope of the liquid crystal layer cross section, the helical axis orientation in the cholesteric phase was not uniformly parallel to the film thickness direction, and the helical pitch was It was confirmed that cholesteric alignments that were not uniformly spaced were formed in the surface region of the liquid crystal layer.

When a He-Ne laser (wavelength 632.8 nm) was incident on the laminate obtained so as to be perpendicular to the plane of the cholesteric alignment film, laser light was emitted at an emission angle of 0 ° and about ± 35 °. Was observed. In order to further confirm the polarization characteristics, the obtained laminate was placed under normal room illumination and observed through a right circularly polarizing plate (transmitting only right circularly polarized light). And the brightness when observed without a polarizing plate was almost the same.
On the other hand, observation through a left circularly polarizing plate (transmitting only left circularly polarized light) revealed a dark field, and no iridescent reflected and diffracted light was observed.

When the laminate obtained under indoor lighting was visually observed, the laminate showed bright gold-colored reflected light with a metallic luster, and had a high-quality texture. It was observed very bright when observed from the specular reflection angle direction, and had the same properties as a mirror surface.

It was confirmed that the laminate obtained from the above functions as a specular polarization diffraction element in which the diffracted light is right-handed circularly polarized light.

Example 2 In the same manner as in Example 1, a diffraction pattern was transferred to a cholesteric alignment film having a diffusion rate of about 9%. Polyester film having a 25 μm-thick silicone release layer on its surface (PET; support substrate 1)
The film and the cholesteric alignment film surface are bonded with a commercially available acrylic photocurable adhesive 1 and only the PPS film is peeled off, and is composed of a cholesteric alignment film layer / photocurable adhesive layer 1 / PET film (support substrate 1). A laminate was obtained.

Next, a commercially available polyester-based hot melt adhesive (adhesive layer 2) was applied to the cholesteric alignment film surface of the laminate, and a 80 μm-thick UV absorber-containing triad was heated with a laminator heated to 100 ° C. Acetylcellulose (TAC) film (U, manufactured by Fuji Photo Film Co., Ltd.)
VD80: laminated with support substrate 2). Support substrate 1 after cooling
Was peeled off to obtain a polarization diffraction element of the present invention. In the obtained polarization diffraction element, rainbow colors due to the diffraction pattern and selective reflection peculiar to the cholesteric liquid crystal were clearly recognized.

Example 3 In the same manner as in Example 1, a diffraction pattern was transferred to a cholesteric alignment film having a diffusion rate of about 9%. Polyester film having a 25 μm-thick silicone release layer on its surface (PET; support substrate 1)
The film and the cholesteric alignment film surface on which the diffraction pattern has been transferred are bonded with a commercially available acrylic photocurable adhesive 1 to which a hard coat agent has been added, only the PPS film is peeled off, and the cholesteric alignment film layer / photocurable adhesive A laminate comprising layer 1 / PET film (support substrate 1) was obtained.

Next, a commercially available polyester-based hot melt adhesive (adhesive layer 2) was applied to the cholesteric oriented film surface of the laminate, and the laminate was in contact with a 1 mm thick polyvinyl chloride sheet on which aluminum was deposited. When transferred by a hot stamp, the support substrate 1 P
The transfer was clearly peeled off from the ET film surface. For the polarized light diffractive element consisting of the cholesteric alignment film / hard coat layer (photo-curable adhesive layer 1) on the transferred polyvinyl chloride sheet, the rainbow color and the cholesteric liquid crystal have a vivid diffraction pattern even with reflected light. Reflection was clearly recognized.

(Example 4) 6.42 g of methylhydroquinone bis (4- (6-acryloyloxyoxyhexyloxy) benzoic acid) ester, which is a positive uniaxial nematic liquid crystal compound, and 4-cyanophenol 4- (6- (Acryloyloxyhexyloxy) benzoic acid ester to 0.
98 g, 2.60 g of a commercially available chiral dopant liquid crystal S-811 (manufactured by Roddick Co., Ltd.) were weighed and distilled and purified.
Dissolved in 90 g of methyl-2-pyrrolidone. To this solution was added 0.5 m of a fluorine surfactant S-383 (manufactured by Asahi Glass Co., Ltd.).
g, photoinitiator Irgacure 907 (manufactured by Ciba Geigy) 0.3 g, sensitizer diethylthioxanthone 0.1 g.
1 g was added, and the surface was applied using a bar coater on a polyethylene naphthalate (PEN) film (manufactured by Mitsubishi Diafoil Co., Ltd.) whose surface was rubbed with a rayon cloth. After coating, the film was put into a clean oven set at 60 ° C. and dried for 15 minutes.
Then, the liquid crystal layer was heat-treated in an oven set for 6 minutes, and cooled from that temperature to 50 ° C. at a rate of about 1 ° C./min to complete the cholesteric alignment of the liquid crystal layer. The thickness of the cholesteric liquid crystal layer measured by a stylus thickness was 1.5 μm.
Next, the cholesteric liquid crystal layer was put into an oven set at 50 ° C. while being formed on the PEN film, and allowed to cool to the oven set temperature under a nitrogen atmosphere having an oxygen concentration of 250 ppm or less, and then UV irradiation was performed at that temperature. Was.
A high-pressure mercury lamp is used as the UV light source, the irradiation intensity is 120 W / cm ^{2 at} the maximum, the irradiation time is 5 seconds, and the integrated irradiation amount is 135.
Irradiation at mJ. The liquid crystal layer after irradiation was hardened to some extent and did not have the fluidity observed before hardening, but its surface hardness was lower than 6B in pencil hardness, and the exact hardness could not be measured.

The cholesteric liquid crystal layer formed on the PEN film was compared with an ultraviolet-visible near-infrared spectrophotometer V-manufactured by JASCO Corporation.
When the transmission spectrum was measured at 570, it was confirmed that a cholesteric orientation exhibiting selective reflection having a center wavelength of about 580 nm and a selective reflection wavelength bandwidth of about 40 nm was formed. The liquid crystal layer was subjected to specular colorimetry CM-3500d manufactured by Minolta Co. to remove specular reflection (SCE).
And the specular reflectance (SCI) were measured.
E5%, SCI 43%, and diffusivity was about 12%. Remove the cholesteric liquid crystal layer on the PEN film taken out of the oven so that the rubbing direction is long.
A cm × 3 cm rectangle was cut out, and a commercially available embossed film J52,989 (manufactured by Edmund Scientific Japan) was cut into a 12 cm × 5 cm rectangle in which the grating direction of the diffraction grating was long. Next, the cholesteric liquid crystal layer side of the cut PEN film is overlapped so that the liquid crystal layer side of the cholesteric liquid crystal layer and the diffraction grating surface of the embossed plate film are in contact with each other. Laminating device D
X-350 (manufactured by Toh Lami). Thermal lamination is
The temperature of the laminating roll was 72 ° C., and the moving speed of the sample was 30 mm / sec. After the heat lamination, the cholesteric liquid crystal layer and the embossed plate film integrally adhered to each other to form a laminate. The laminate was cooled to room temperature, and the cholesteric liquid crystal layer side was irradiated with an electron beam (EB) at room temperature. The EB irradiation was performed using an EB irradiator manufactured by Eye Electron Beam Co., Ltd. at room temperature and in an atmosphere with an oxygen concentration of 0.20% at an acceleration voltage of 30 kV. After the EB irradiation, the embossed plate film was peeled off from the laminate along the film longitudinal direction.
The cholesteric liquid crystal layer remaining on the supporting PEN film after EB irradiation was cured, and its surface hardness was about 2H in terms of pencil hardness.

Polyester film having a 25 μm-thick silicone release layer on its surface (PET; support substrate 1)
The film and the cholesteric alignment film surface from which the embossed plate film was peeled off were adhered with a commercially available acrylic photocurable adhesive 1, only the PEN film was peeled off, and the cholesteric liquid crystal layer / photocurable adhesive layer 1 / PET film ( A laminate composed of the support substrate 1) was obtained.

Then, a commercially available polyester-based hot melt adhesive (adhesive layer 2) was applied to the cholesteric liquid crystal layer surface of the laminate, and a UV absorber-containing triacetyl having a thickness of 80 μm was applied by a laminator heated to 100 ° C. Cellulose (TAC) film (UVD manufactured by Fuji Photo Film Co., Ltd.)
80; laminated with support substrate 2). After cooling, the P
The ET film was peeled off to obtain a laminate.

When the obtained laminate was visually observed, it showed a golden reflected light with a colorful metallic luster.
The reflected light was observed very bright when viewed from the specular reflection angle direction, and had the same properties as the mirror surface. Also, the liquid crystal layer, apart from the reflected light caused by cholesteric alignment,
When the film was viewed obliquely from the 3 o'clock and 9 o'clock directions when the longitudinal direction of the film was viewed at the 12 o'clock direction, iridescent light characteristic of the diffraction grating was observed.

When the orientation state of the cholesteric liquid crystal layer of the obtained laminate was observed by a polarizing microscope and a transmission electron microscope of a cross section of the liquid crystal layer, it was found that the helical axis direction in the cholesteric phase was uniformly parallel to the film thickness direction. It was confirmed that a cholesteric alignment in which the helical pitch was not uniform and the helical pitch was not uniformly spaced in the film thickness direction was formed in the surface region of the liquid crystal layer. When a He / Ne laser was vertically incident on the laminate, 0 ° and about ± 9 ° emission angles
Second and ± 1st order diffracted lights were observed. Next, in order to confirm the polarization characteristics, the obtained laminate was placed under normal room illumination and observed through a left circularly polarizing plate (transmitting only left circularly polarized light). , A bright gold reflected color was observed at the same time, which was almost the same as the brightness when observed without a polarizing plate. In contrast, observation through a right circularly polarizing plate (transmitting only right circularly polarized light) showed a dark field, and neither rainbow-colored reflected diffracted light nor reflected color due to cholesteric liquid crystal was observed.

It was confirmed that the laminate obtained as described above functions as a specular polarization diffraction element in which the diffracted light is right circularly polarized light.

[0093]

According to the present invention, it is possible to manufacture a non-specular polarization diffraction element having a unique optical property that diffracted light exhibits circular polarization without performing complicated steps and processing. In addition, since it is specular, a vivid coloration effect with a metallic luster can be exhibited, and a polarization diffraction element having extremely excellent design properties can be obtained. Further, according to the production method of the present invention, the surface area of the cholesteric alignment film exhibiting diffractive ability can be appropriately selected on the viewing side or on the side opposite to the viewing side, so that it can be selected according to the optical characteristics required for its use. A polarization diffraction element can be obtained. Therefore, the polarization diffraction element obtained by the manufacturing method of the present invention has a very wide range of application as a diffraction function element, for example, an optical element such as a liquid crystal display, an optoelectronic element, a decoration material, and a forgery prevention element. And the like can be suitably used as an optical member.

Claims (4)

[Claims] 1. The method according to claim 1, wherein a ratio of the regular reflection removal reflectance (SCE) to the regular reflection reflection ratio (SCI) ((SCC)
E / SCI) × 100) a first step of forming a cholesteric alignment film having a diffusivity of less than 15%,
A second step of transferring the diffraction pattern of the diffraction element substrate onto the cholesteric alignment film surface, a third step of laminating the cholesteric alignment film surface to which the diffraction pattern has been transferred and the support substrate 1 via the adhesive layer 1, a first step; A fourth step of removing the alignment support substrate used in the step from the cholesteric alignment film, and a fifth step of laminating the cholesteric alignment film surface from which the alignment support substrate has been removed and the support substrate 2 via the adhesive layer 2. A method for manufacturing a polarization diffraction element. 2. A sixth step of removing the support substrate 1 used in the third step from the cholesteric alignment film after laminating the cholesteric alignment film surface from which the alignment support substrate has been removed and the support substrate 2 via an adhesive layer. The method for producing a polarization diffraction element according to claim 1, comprising: 3. The method for producing a polarization diffraction element according to claim 2, further comprising a seventh step of, after peeling and removing the supporting substrate 1, forming a protective layer on the cholesteric alignment film surface from which the substrate has been peeled and removed. 4. The method according to claim 3, wherein the protective layer has an ultraviolet absorbing property and / or a hard coating property.