KR102030270B1 - Method of manufacturing organic el image display device - Google Patents

Abstract

A method of manufacturing an organic EL image display device comprising adhering a light emitting element substrate including an organic electroluminescent layer arranged in a matrix form and an optical functional resin layer including a portion corresponding to the organic electroluminescent layer in a matrix form. The manufacturing method which does not produce wrinkles and does not produce the position shift of each organic electroluminescent layer and each optical functional resin layer is provided.
A step of providing an adhesive layer on the surface of the film or the surface of the light emitting device substrate including the optical functional resin layer, the film facing the light emitting device substrate, and the organic electroluminescent layer and the corresponding portion of the And a step of curing the adhesive layer by ultraviolet irradiation or the like in the aligned state, wherein the adhesive layer is provided by transfer.

Description

The manufacturing method of organic electroluminescent image display apparatus {METHOD OF MANUFACTURING ORGANIC EL IMAGE DISPLAY DEVICE}

The present invention relates to a method for producing an organic EL image display device.

Image performance in an organic EL image display device ("organic electroluminescent image display device", hereinafter sometimes referred to simply as "image display device") that forms an image based on light emission of an organic electroluminescent layer arranged in a matrix shape. In order to improve, various optical functional resin layers are provided in the image display surface.

For example, in order to reduce the surface reflection of external light and to improve contrast, it is common to arrange the circularly polarizing plate which consists of a phase difference layer and a polarizing layer. Moreover, the prevention of the fall of the luminance by arrangement | positioning of a circularly polarizing plate further using the polarization separation layer is proposed (for example, patent document 1).

In the organic EL image display device described in Patent Literature 1, the cholesteric liquid crystal layer is patterned by adjusting the selective reflection wavelength in a wavelength range corresponding to the light emitted from the organic electroluminescent layer, so that each organic electroluminescent layer and each cholesteric It is necessary to laminate | stack a polarization separation layer on an image display surface by aligning so that a liquid crystal layer may correspond.

As a method of alignment in lamination of a film member, Patent Document 2 discloses a method of using a substrate on which a alignment pattern is formed and a film member on which a alignment pattern is formed. In this method, the curable adhesive layer is provided on the film member by coating, and then, the curable adhesive layer is cured stepwise from the vicinity of the alignment pattern to bond the substrate and the film member.

Japanese Unexamined Patent Publication No. 2016-149372 Japanese Unexamined Patent Publication No. 2002-113784

In general, in order to prevent wrinkles from occurring when the resin film is adhered to a substrate such as a light emitting element substrate, it is common to apply a tension to the resin film and bond it in an expanded state. However, as described in Patent Literature 1, when the polarization splitting layer comprising the cholesteric liquid crystal layer in a matrix form is bonded to the light emitting element substrate by performing the above-mentioned alignment in a state where the tension is loaded, the residual stress in the tension load direction is reduced. By this, it is considered that the aligned position is shifted. Moreover, in the method of patent document 2, wrinkles may arise in an optical member in the process of hardening.

The present invention provides an organic EL image display device comprising adhering a light emitting element substrate including an organic electroluminescent layer arranged in a matrix form and an optical functional resin layer including a portion corresponding to the organic electroluminescent layer in a matrix form. The method WHEREIN: It is a subject to provide the manufacturing method which does not produce wrinkles in an optical functional resin layer or the film containing this, and does not produce the position shift of each organic electroluminescent layer and each optical functional resin layer.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject, discovered the position alignment means and the subsequent bonding means which solve the said subject, and completed this invention based on the obtained discovery.

That is, this invention provides the following [1]-[11].

[1] A method for manufacturing an organic EL image display device comprising a light emitting element substrate having an organic electroluminescent layer arranged in a matrix and an optically functional resin layer comprising a portion corresponding to the organic electroluminescent layer in a matrix form.

Providing an adhesive layer on any one surface of a film containing said optical functional resin layer or one surface of said light emitting element substrate,

Placing the film on the light emitting element substrate so that the adhesive layer is disposed between the film and the light emitting element substrate, and performing alignment of the organic electroluminescent layer and the corresponding portion while applying tension to the film; and

Bonding the film to the light emitting device substrate by curing the adhesive layer using heating or ultraviolet irradiation in the aligned state;

And said adhesive layer is provided by transfer from a transfer film comprising said adhesive layer.

[2] The production method according to [1], wherein the film is in a roll shape, and the direction of the tension load is in the major axis direction of the film.

[3] The production method according to [1] or [2], wherein the light emitting element substrate is in a roll shape and the direction of the tension load is in the major axis direction of the light emitting element substrate.

[4] The production method according to any one of [1] to [3], including the step of providing the adhesive layer on either surface of the light emitting element substrate.

[5] The production method according to any one of [1] to [4], wherein the thickness of the adhesive layer is 2.0 µm to 30 µm.

[6] The production method according to any one of [1] to [5], in which the adhesive layer includes a thermoplastic resin having a weight average molecular weight of 50,000 to 500,000, a polymerizable compound containing an ethylenically unsaturated double bond, and a polymerization initiator. .

[7] The production method according to [6], wherein the adhesive layer further contains a fluorine-based surfactant.

[8] The production method according to any one of [1] to [7], wherein the curing is curing by ultraviolet rays.

[9] The optical functional resin layer is a polarization separation layer,

[1] to [8], wherein the site is a polarization separation site that reflects light in one polarization state and transmits light in the other polarization state among the light emitted by the corresponding organic electroluminescent layer. The manufacturing method of one.

[10] The production method according to [9], wherein the polarization separation site is formed of a layer formed by fixing a cholesteric liquid crystal phase.

[11] the film further comprises a retardation layer and a polarizing layer,

The manufacturing method as described in [9] or [10] in which the said polarization separation layer, the said retardation layer, and the said polarizing layer are arrange | positioned in this order from the said facing surface side.

According to the present invention, there is provided an organic EL image display device comprising adhering a light emitting element substrate including an organic electroluminescent layer arranged in a matrix form and an optical functional resin layer including a portion corresponding to the organic electroluminescent layer in a matrix form. In the manufacturing method, the manufacturing method which does not produce wrinkles in an optical functional resin layer, and does not produce the position shift of each organic electroluminescent layer and each optical functional resin layer is provided.

1 is a view schematically showing a mask used in the embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

In the present specification, the numerical display, the numerical range, and the qualitative expression (for example, expressions "all", "same", "same", etc.) refer to an image display device or a member used therefor. It is to be interpreted that the numerical value, the numerical range, and the property including the generally allowable error are expressed.

In the present specification, for example, an angle such as "45 °", "parallel", "vertical", or "orthogonal" means that the difference from the exact angle is within a range of less than 5 ° unless otherwise specified. . It is preferable that it is less than 4 degrees, and, as for the difference with an exact angle, it is more preferable that it is less than 3 degrees.

In this specification, "(meth) acrylate" is used by the meaning of "any one or both of an acrylate and a methacrylate." The same applies to "(meth) acrylic acid" and the like.

In the present specification, the term "sense" with respect to circularly polarized light means right circularly polarized light or left circularly polarized light. The sense of circularly polarized light is defined as the right circularly polarized light when the tip of the full length vector rotates clockwise as time passes and the counterclockwise rotation is defined as the left circularly polarized light. .

In this specification, the term "sense" may be used with respect to the twisting direction of the spiral of the cholesteric liquid crystal. When the twist direction (sense) of the spiral of the cholesteric liquid crystal is right, it reflects right circularly polarized light, and when the sense is left, it reflects left circularly polarized light and transmits right circularly polarized light.

Visible light is the light of the wavelength which can be seen by a human eye among electromagnetic waves, and shows the light of the wavelength range of 380 nm-780 nm.

In this specification, the visible light transmittance should just be measured based on JISA5759: 2008. The visible light transmittance can be measured using, for example, an ultraviolet visible near infrared spectrometer (manufactured by Nihon Bunco Co., Ltd., V-670, integrating sphere unit ISN-723).

In addition, in this specification, a visible light reflectance means the numerical value computed based on the calculation method as described in JIS A5759. In other words, the spectrophotometer measures the reflectance with a wavelength of 380 nm to 780 nm, multiplies the spectral distribution of the CIE (International Illumination Commission) daylight D65, the wavelength distribution of the CIE bright standard non-sensitivity, and the weighted coefficient obtained from the wavelength spacing to perform a weighted average of the visible light reflectance. Obtain

When obtaining visible light reflectance, the spectrophotometer "V-670" made from Nippon Bunko Corporation can be used, for example.

<Method for Manufacturing Organic EL Image Display Device>

The organic EL image display device is a self-luminous display device, and has an advantage of display performance such as high visibility and no viewing angle dependency compared to a CRT (Cathode Ray Tube) type display device or a liquid crystal display device. There are also advantages such as weight reduction and thickness reduction. An organic EL image display apparatus performs image display by the light emitting element substrate in which the organic electroluminescent layer group was provided.

The organic EL image display apparatus manufactured by the manufacturing method of this invention contains the light emitting element substrate in which the organic electroluminescent layer was arrange | positioned in matrix form, and the optical functional resin layer containing the site | part corresponding to the organic electroluminescent layer in matrix form. In the organic EL image display device manufactured by the manufacturing method of the present invention, an adhesive layer is further included between the light emitting element substrate and the optical functional resin layer. In addition, in this specification, the term adhesive layer is used also when showing any of the adhesive layer after hardening, and the adhesive layer before hardening (layer formed by the composition for adhesive layer formation mentioned later). Which is clear from a context, For example, in the manufacturing method of this invention, the contact bonding layer provided in either the surface of the film containing an optical functional resin layer or the surface of the light emitting element substrate is a thing before hardening. It is an adhesive layer.

The organic electroluminescent image display apparatus manufactured by the manufacturing method of this invention may contain other layers of that excepting the above.

The manufacturing method of the present invention,

Providing an adhesive layer on either surface of a film containing an optical functional resin layer or on either surface of a light emitting element substrate,

Placing the film on the light emitting device substrate so that the adhesive layer is disposed between the film and the light emitting device substrate, and performing alignment of the organic electroluminescent layer and the corresponding portion while applying tension to the film; And

And curing the adhesive layer by heating or ultraviolet irradiation in the aligned state.

Hereinafter, the material and procedure used in each process are demonstrated.

[Light Emitting Device Substrate]

As the light emitting element substrate, one in which the organic electroluminescent layer is arranged in a matrix form is used. Usually, a light emitting element substrate should just be a thing including a reflection layer and an organic electroluminescent layer on the TFT board | substrate which has a pixel structure formed by the thin film transistor (TFT) etc. on the surface, such as glass.

In the image display device of monochromatic light emission, all of the organic electroluminescent layers included in the organic electroluminescent layer group may emit light having the same wavelength. On the other hand, it is preferable that the organic electroluminescent layer group usually includes an organic electroluminescent layer which emits light of different wavelengths, and more preferably includes two or more organic electroluminescent layers, in particular three or more organic electroluminescent layers. It is preferable that an organic electroluminescent layer group contains the organic electroluminescent layer of red luminescence, the organic electroluminescent layer of green luminescence, and the organic electroluminescent layer of blue luminescence.

In the light emitting element substrate, when the TFT substrate, the reflective layer, and the organic electroluminescent layer are arranged in this order, the image display device can take out light by top emission method and display the image. In the light emitting element substrate, when the TFT substrate, the organic electroluminescent layer, and the reflective layer are arranged in this order, the image display device can take out light by displaying a bottom emission method and display the image. Although the top emission system or the bottom emission system may be sufficient as the image display apparatus of this invention, it is preferable that it is a top emission system.

The reflective layer may be, for example, a reflective electrode. As the reflective electrode, an aluminum electrode generally used in an organic electroluminescent device can be used. The light emitting device substrate further includes a transparent electrode such as an indium tin oxide (ITO) electrode. As an example of the layer structure in a light emitting element substrate, the following is mentioned.

Layer Composition 1: TFT Substrate / Reflective Electrode / Organic Electroluminescent Layer / Transparent Electrode

Layer Composition 2: TFT Substrate / Transparent Electrode / Organic Electroluminescent Layer / Reflective Electrode

The light emitting element substrate may further include a barrier layer, a light extraction layer, and the like for sealing the organic electroluminescent layer.

By providing a barrier layer, the organic electroluminescent layer which is weak in moisture can be sealed and a trace amount of moisture can also be blocked. The barrier layer should normally be provided so that a TFT substrate, an organic electroluminescent layer, and a barrier layer may be in this order.

In the manufacturing method of this invention, when the light emitting element substrate adhere | attaches the film containing an optical functional resin layer, when it is a light emitting element substrate of the said laminated constitution 1, it is preferable that it is a barrier layer or a transparent electrode. In the case of the light emitting element substrate of the layer structure 2, what is necessary is just the surface (surface on the opposite side to the surface in which TFT is provided) of a TFT substrate.

The light emitting element substrate may be prepared in a roll shape in order to be able to perform a tension load described later using a laminator, but may not be in a roll shape.

[Organic Electroluminescent Layer]

The organic electroluminescent layer has at least a light emitting layer, and may further include layers which may include respective layers such as a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer and an electron injection layer as functional layers other than the light emitting layer. it means.

As an organic electroluminescent layer, you may use the organic electroluminescent layer of the micro cavity structure of Unexamined-Japanese-Patent No. 2016-139372.

About the organic electroluminescent layer, each layer in an organic electroluminescent layer, the manufacturing material and structure of a transparent electrode and a reflective electrode, a lamination | sequence order, and the structure of a light emitting element substrate, Paragraph 0081-0122 of Unexamined-Japanese-Patent No. 2012-155177, a Japanese patent See Japanese Unexamined Patent Publication No. 4012992 and Japanese Unexamined Patent Application Publication No. 2016-139372.

[Optical Functional Resin Layer]

In this specification, an optically functional resin layer means the layer which contains the site | part corresponding to the organic electroluminescent layer in the light emitting element substrate used in combination in the manufacturing method of this invention in matrix form. In this specification, a correspondence is a state in which the organic electroluminescent layer and the said part are in the same position or the position which at least one part overlaps with each other when the image display apparatus manufactured by the manufacturing method of this invention is seen from the image display side. Means that.

As an example of an optical functional resin layer, the polarization separation layer mentioned later is mentioned. Moreover, the polarization separation site mentioned later is mentioned as an example of said corresponding site | part.

The corresponding organic electroluminescent layer and the said site | part may be the same size, the size of the organic electroluminescent layer may be large, and the size of the said site | part may be large. Especially, when the said site | part is a polarization separation site, it is preferable that the size of a polarization separation site is larger than the size of an organic electroluminescent layer. It is preferable that it is the size which an organic electroluminescent layer covers on the corresponding polarization separation site when seen from the image display side.

The film containing the optical functional resin layer used for the manufacturing method of this invention may contain layers other than an optical functional resin layer. For example, when the optical functional resin layer is a polarization separation layer, the film containing the optical functional resin layer may further include a phase difference layer, a polarization layer, or a circular polarizing plate. Moreover, the adhesive layer for adhesion of any one of these layers and an optical functional resin layer may be included.

The film containing the optically functional resin layer is prepared to include the site at a pitch smaller than the pitch of the organic electroluminescent layer in the direction parallel to the direction of the tension load in the tension unloaded state of the present invention. It is preferable to be prepared to include the said site | part in the pitch of the same direction of 99.0 to 99.99%. In the stage of preparation of the film containing an optical functional resin layer, it uses the film which formed the optical functional resin layer so that the said site | part may be included in small pitch with respect to the pitch of the organic electroluminescent layer in the light emitting element board | substrate adhere | attached, By adjusting the pitch in the direction of the tension load of the site and the pitch of the organic electroluminescent layer in a state where the film is slightly stretched under tension, the alignment method can be performed while the tension is loaded in the manufacturing method of the present invention. Because. In the present specification, the tension unloaded state means a state in which tension is not applied, and, for example, a state in which a roll is loosened means a film prepared in a roll shape.

As for the pitch of the said site with respect to the pitch of an organic electroluminescent layer, it is more preferable that it is 99.9 to 99.99%.

The film containing the optical functional resin layer may be prepared as a film provided on the surface of a support or the like. The support may be peeled off before positioning or bonding described later.

Moreover, in order to enable the film containing an optical functional resin layer to perform the tension load mentioned later using a laminator, it is preferable to prepare in roll shape.

[Positioning, tension load]

The film containing the optical functional resin layer is faced with the light emitting element substrate, and the organic electroluminescent layer of matrix shape and the said site | part of the said matrix shape are performed, loading a tension on a film.

Although the method of tension load is not specifically limited, Usually, what is necessary is just to carry out by the tension (web tension) loaded with the laminator used at the time of adhesion | attachment of a film and a light emitting element substrate. Adjustment of the strength of tension in the method of tension load using a laminator can be performed by the tension controller of a laminator.

As a laminator, Hitachi Industries, Ltd. (Lamic II type) etc. can be used.

It is preferable to carry out so that tension load may be 0.01%-1.0%, and it is more preferable to carry out so that it may become 0.01 to 0.1%.

Thereby, the position shift of an organic electroluminescent layer and an optical functional resin layer can be prevented from accumulating. For example, in the case where there is a 0.1% pitch deviation due to the stretching of the film, if the pitch is not adjusted in the case of aligning the film to a 50 cm long substrate, the positional deviation of 500 µm or more at the end of the substrate This happens. In the organic EL image display device, since the size of the light emitting layer is about 50 µm, it is important to eliminate this deviation. Moreover, although the position shift on the edge part side of a board | substrate becomes large, so that the size of the board | substrate to be used increases, this can be improved by the manufacturing method of this invention.

When the film containing an optical functional resin layer is roll shape, it is preferable to make the direction of a tension load into the major axis direction of the said film. At this time, the tension may or may not be loaded in the direction orthogonal to this.

Moreover, when a light emitting element substrate is in roll shape, it is preferable to make the direction of the tension load with respect to the said film into the long axis direction of a light emitting element substrate.

Positioning is performed so that the site | part in an organic electroluminescent layer in a light emitting element substrate may correspond. The organic electroluminescent layer disposed in the range necessary for fabrication of the organic EL image display device and the above-mentioned portions may be aligned so as to correspond to each other.

Positioning can be performed by a well-known method. For example, the method of Unexamined-Japanese-Patent No. 2007-187926 can also be taken.

You may perform bonding together or after alignment with alignment. Bonding means making the film containing an optically functional resin layer, and a light emitting element substrate contact with each other via an adhesive layer. Bonding should just be performed before adhesion (hardening). Bonding can be performed by the bonding apparatus (laminator) which has a roller for bonding inside, for example.

[Adhesion, hardening]

In the manufacturing method of this invention, the film containing an optical functional resin layer, and a light emitting element substrate are bonded by the state aligned. That is, it is adhere | attached as it is in the state in which the tension was loaded to the film.

Adhesion is performed by hardening the contact bonding layer arrange | positioned between the film containing an optical functional resin layer, and a light emitting element substrate using heating or ultraviolet irradiation. It is preferable to perform hardening to the whole surface simultaneously about hardening part.

Curing may be photocuring based on thermosetting or ultraviolet irradiation, depending on the adhesive layer used. Among these, photocuring is preferable. This is because it is easy to cure while maintaining the loaded tension.

What is necessary is just to perform thermosetting by heating at 80 degreeC-200 degreeC, Preferably it is 90 degreeC-150 degreeC.

20mJ / cm <^2> -3000mJ / cm <^2> is preferable and, as for the ultraviolet irradiation energy in photocuring, 100mJ / cm <^2> -1000mJ / cm <^2> is more preferable. You may perform light irradiation under heating conditions or nitrogen atmosphere. The irradiation ultraviolet wavelength is preferably 350 nm to 430 nm.

Since the hardening is performed on the entire surface at the same time, for example, the UV irradiation device or the heating device is provided immediately after the bonding roller in the bonding device, and the curing of the adhesive layer is performed immediately after bonding. I can do it. By such a procedure, the adhesive layer can be cured in a state where the tension is loaded on the film and aligned. In particular, it is preferable to provide an ultraviolet irradiation device. It is because the fall of the positional precision by thermal expansion can be avoided by hardening of the contact bonding layer by an ultraviolet-ray.

Arrangement of an adhesive layer is performed by providing an adhesive layer on either the surface of the film containing an optical functional resin layer, or the surface of either light emitting element substrate. In particular, it is preferable to provide an adhesive layer on either surface of the light emitting element substrate before positioning. This is because wrinkles and positional shifts derived from the adhesive layer after curing are hardly generated by providing the adhesive layer in advance on a light emitting element substrate having a higher elastic modulus. In the manufacturing method of this invention, an adhesive layer is provided in any one of said surfaces by transferring an adhesive layer from the transfer film containing a support body and an adhesive layer. Specifically, for example, the transfer is performed by bringing the adhesive layer side of the transfer film including the branch support and the adhesive layer into contact with any one of the above surfaces, and then peeling the branch support.

It is preferable that they are all 2.0 micrometers-30 micrometers, and, as for the thickness of an adhesive layer and the adhesive layer after hardening, it is more preferable that they are 5.0 micrometers-20 micrometers.

[Composition of Adhesive Layer]

The composition of the adhesive layer is not particularly limited, and a curing type adhesive agent used for forming the adhesive layer described later can be used.

Moreover, in the manufacturing method of this invention, the composition of the thermoplastic resin layer of Unexamined-Japanese-Patent No. 2003-228165 can also superpose | polymerize the function of hardening by light or a thermal polymerization initiator, and a plasticizer and light or heat, and can superpose | polymerize. It is also preferable to use the thermoplastic resin layer of the following composition which added the polymeric compound which has an unsaturated double bond as an adhesive layer.

(Thermoplastic layer)

The thermoplastic resin layer contains at least a thermoplastic resin, a polymerization initiator, and the polymerizable compound. The thermoplastic resin layer may contain other components as needed.

Examples of the thermoplastic resin include a saponified product of ethylene and an acrylic acid ester copolymer, a saponified product of a styrene and an (meth) acrylic acid ester copolymer, a saponified product of a vinyltoluene and a (meth) acrylic acid ester copolymer, a poly (meth) acrylic acid ester, and It is preferable that it is at least 1 sort (s) chosen from saponified products, such as (meth) acrylic acid ester copolymers, such as butyl (meth) acrylic acid and vinyl acetate. These may be used individually by 1 type and may use 2 or more types together. Moreover, it is preferable that the softening point is 80 degrees C or less among these thermoplastic resins.

In the said thermoplastic resin, Preferably resin of the range of the weight average molecular weights 50,000-500,000 (Tg = 0-140 degreeC), More preferably, the weight average molecular weights 60,000-200,000 (Tg = 30-110 degreeC) Resin of the range of can be selected and used. As a specific example of these resin, the methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer of Unexamined-Japanese-Patent No. 63-147159 is mentioned.

Moreover, in said various resin, Preferably it is resin of the range of the weight average molecular weights 3000-30,000 (Tg = 30-170 degreeC), More preferably, the weight average molecular weights 40-20,000 (Tg = 60-140). Resin in the range of ° C) can be selected and used. As a preferable specific example, the styrene / (meth) acrylic acid copolymer as described in each of Unexamined-Japanese-Patent No. 55-38961 and Unexamined-Japanese-Patent No. 5-241340 is mentioned.

Resin of the range of the weight average molecular weights 3000-30,000 (Tg = 30-170 degreeC) can be used together with resin of the range of said weight average molecular weights 50,000-500,000 (Tg = 0-140 degreeC).

The polymeric compound which has an ethylenically unsaturated double bond should just be a polymeric compound which can superpose | polymerize by irradiation of light or heat. As a polymeric compound which has an ethylenically unsaturated double bond, the compound which has an ethylenically unsaturated group which can be at least 1 addition polymerization in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. For example, monofunctional acrylates, such as polyethyleneglycol mono (meth) acrylate, polypropyleneglycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate, and monofunctional methacrylate, polyethyleneglycol Lycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tri Methylol propane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth ) Acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane Rai (acryloyloxyethyl-propyl) ether, tri (acryloyloxyethyl) isopropoxide between isocyanurate, tri (acryloyloxyethyl) between cyanurate, glycerin tri (meth) acrylate; And polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding propylene oxide to ethylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated.

The polymerizable compound having an ethylenically unsaturated double bond can also function as a plasticizer.

As a polymerization initiator, a photoinitiator or a thermal polymerization initiator is used according to a hardening method, and it is preferable to use a photoinitiator.

As a photoinitiator, it is preferable to use a radical polymerization initiator.

As an example of a radical polymerization initiator, Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irga) marketed by BASF Corporation Cure 369, Irgacure 379, Irgacure 819, etc., Darocure series (e.g., Tarocure TPO, Tarocure 1173, etc.), Quantacure PDO, from Lamberti Commercially available Esacure series (e.g. Ezacure TZM, Ezacure TZT, Ezacure KTO46, etc.), Ezacure KIP series, and the like.

As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile (available as Wako Junyaku V-60 or Otsuka Kagaku AIBN), 2,2'-azobis- (2,4 Dimethylvaleronitrile) (available as Wako Junyaku V-65 or Otsuka Kagaku ADVN), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) (Available as Wako Junyaku V-70) and the like, or a water-soluble organic azo compound.

The polymerization initiator should just be contained in 0.5 mass%-10.0 mass% with respect to the mass of a thermoplastic resin, Preferably it is 1 mass%-5 mass%.

In the thermoplastic resin layer, other polymers, plasticizers, supercooled substances, and adhesion improving agents, in addition to the thermoplastic resin and the polymerization initiator, are used within the range of substantially no softening point exceeding 80 ° C. for the purpose of controlling the adhesive force with the support or the release layer. , Surfactant, mold release agent and the like can be added. By these, adjustment of Tg is also possible. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, and polyethylene glycol. Mono (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, epoxy resin and polyethylene glycol mono Addition reaction product of (meth) acrylate, addition reaction product of organic diisocyanate and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction product of bisphenol A with polyethylene glycol mono (meth) arc There may be mentioned the condensation reaction product of the rate. As for the quantity of a plasticizer in an alkali-soluble thermoplastic resin layer, 200 mass% or less is common with respect to a thermoplastic resin, and the range of 20-100 mass% is preferable.

Surfactant can be used as long as it is mixed with a thermoplastic resin. Preferable surfactants include various known fluorine-based surfactants and silicone-based surfactants (fluorine-based surfactants or silicone-based surfactants, surfactants containing both fluorine atoms and silicon atoms). You may use combining these 2 or more types of surfactant. Of these, fluorine-based surfactants are most preferred.

1-38 are preferable, as for the number of fluorine atoms of the fluorine-containing substituent in the molecule | numerator of a fluorine-type surfactant, 5-25 are more preferable, and 7-20 are the most preferable.

As an especially preferable surfactant, the air containing the monomer represented by the following general formula (a) and general formula (b), and whose mass ratio of general formula (a) / general formula (b) is 20/80-60/40 The thing containing coalescence is mentioned.

[Formula 1]

(In formula, R <^1> , R <^2> and R <^3> represent a hydrogen atom or a methyl group each independently. N represents the integer of 1-18, m represents the integer of 2-14. P represents the integer of 0-18. It does not include the case where p is zero at the same time.)

Moreover, the following commercially available surfactant can also be used as it is. As a commercially available surfactant which can be used, for example, F-top EF301, EF303 (made by Shin-Akita Kasei Co., Ltd.), fluoride FC430, 431 (made by Sumitomo 3M Co., Ltd.), Megapak F-780, F171, F173 , F176, F177, F189, F-554, R08 (manufactured by DIC Corporation), Supron S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) Or silicone surfactants. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Trozol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicone surfactant.

[Transfer film]

When using the thermoplastic resin layer of said composition as an adhesive layer, the transfer film can be obtained by apply | coating the mixture of said each component melt | dissolved in the solvent as needed, and drying a coating film. Moreover, you may provide a peeling layer on a support body as needed.

Examples of the solvent include alcohols such as methanol and ethanol, ketone solvents such as methyl ethyl ketone and acetone, ester solvents such as ethyl acetate, and mixed solvents thereof.

Examples of the branch body include polyester films such as polyethylene terephthalate (PET) films, polycarbonate films, acrylic resin films, epoxy resin films, polyurethane films, polyamide films, polyolefin films, cellulose derivative films, silicone films, and the like. Can be mentioned. Moreover, as a peeling layer, it can select from fluorine resin, silicone resin, silicone fluoride resin, etc., and can use.

Although it does not specifically limit about the method of transferring an adhesive layer to the surface of a light emitting element substrate or the film surface containing an optical functional resin layer using a transfer film, Unexamined-Japanese-Patent No. 2000-334836 and 2002-148794 The method described in each of Unexamined-Japanese-Patent No. 7-110575 and Unexamined-Japanese-Patent No. 11-77942 can be referred.

[Other adhesive layers]

The image display apparatus of this invention may include the other adhesive layer for adhesion | attachment of each layer. Examples of the adhesive used for forming the adhesive layer include a hot melt type, a thermosetting type, a photocuring type, a reaction curing type, and a pressure-sensitive adhesive type that does not require curing. The materials are acrylate, urethane, and urethane, respectively. Acrylate type, epoxy type, epoxy acrylate type, polyolefin type, modified olefin type, polypropylene type, ethylene vinyl alcohol type, vinyl chloride type, chloroprene rubber type, cyanoacrylate type, polyamide type, polyimide type, polystyrene Compounds, such as a polyvinyl butyral type, can be used. From the viewpoint of workability and productivity, a photocuring type, particularly an ultraviolet curing type, is preferable as the curing method, and from the viewpoint of optical transparency and heat resistance, the material is an acrylate type, a urethane acrylate type, an epoxy acrylate type, or the like. Preference is given to using.

It is preferable that it is 0.1 micrometer-10 micrometers, and, as for the thickness of another adhesive layer, it is more preferable that it is 0.5 micrometer-5.0 micrometers.

[Example of Optical Functional Resin Layer: Polarization Separation Layer]

The polarization separation layer is a layer including a polarization separation site.

In this specification, a polarization separation part means the part which performs polarization separation in the wavelength range of the light emission of the corresponding organic electroluminescent layer. Polarization separation means reflecting the light of one polarization state and transmitting the light of the other polarization state. Polarization separation reflects linearly polarized light in one polarization direction, transmits linearly polarized light in the polarization direction orthogonal to the polarization direction, or reflects circularly polarized light in one sense, and the circle of the other sense. What is necessary is just to transmit polarized light.

The organic EL image display device generally includes a circularly polarizing plate composed of a phase difference layer and a polarizing layer on the image display side of the organic electroluminescent layer group in order to reduce surface reflection of external light and to improve contrast. In this configuration, more than half of the light emitted from the organic electroluminescent layer is absorbed by the circularly polarizing plate, but the luminance can be further improved by using a polarization separating layer. This is because the polarization separation layer transmits light that passes through the polarization layer, reflects the polarization absorbed by the polarization layer, and reflects the specular surface in the reflective layer in the light emitting element substrate.

A polarization separating layer can be provided between a light emitting element substrate and a circularly polarizing plate, or between a phase difference layer and a polarizing layer. In the organic EL image display device having the polarization separating layer, the reflective layer, the organic electroluminescent layer, the polarization separating layer, and the circular polarizing plate are arranged in this order.

The polarization separation site may be a site that can selectively perform polarization separation in the wavelength range of light emission of the corresponding organic electroluminescent layer, or may be a site that can perform polarization separation in wavelength ranges other than the wavelength range. "Selective polarization separation" refers to polarization separation in the wavelength range corresponding to the wavelength range of light emission of the organic electroluminescent layer to which the polarization separation site corresponds in the visible light region. Therefore, the polarization separation site may be polarized separation only in the wavelength range corresponding to the wavelength range of the emission of the organic electroluminescent layer to which the polarization separation site corresponds in the visible light region, and substantially polarize separation in the entire wavelength range of the visible light. The polarization separation may be performed in a plurality of wavelength ranges such as a red wavelength band, a green wavelength band, and a blue wavelength band.

The polarization separation layer in the image display device of the present invention includes a plurality of polarization separation sites corresponding to the plurality of organic electroluminescence layers of the organic electroluminescence layer group. In the corresponding organic electroluminescent layer and the polarization separation site, the light emission from the organic electroluminescent layer (preferably in the total amount of light emission, preferably 50% or more, more preferably 60% or more, even more preferably 70% or more) is polarized What is necessary is just a state which has reflected or transmitted at the separation site.

In the corresponding organic electroluminescent layer and the polarization separation site, the wavelength range of the reflection of the polarization separation site is preferably wider than the wavelength range of the emission of the organic electroluminescence layer. This is because in the organic EL image display device satisfying such a relationship, the luminance is improved not only in the front but also in the inclination direction.

The polarization separation site and the polarization separation layer may each be a single layer or may consist of a plurality of layers. It is preferable that a polarization separation part and a polarization separation layer include the polarizer, the wire grid polarizer, or the cholesteric liquid crystal layer which laminated | stacked the thin film from which birefringence differs, for example. In addition to any of these layers, the polarization separation site and the polarization separation layer may include an alignment layer, a protective layer (additive layer), and the like. The polarization separation site and the polarization separation layer may include an optically isotropic layer formed by curing the composition used for forming the cholesteric liquid crystal layer in a state where the liquid crystal compound is not oriented.

The polarization separation site is not particularly limited as long as it achieves the above-mentioned property of reflecting light in one polarization state and transmitting light in the other polarization state among the light emitted by the organic electroluminescent layer, but is cholesteric It is preferable that it is a site | part containing a liquid crystal layer.

The polarization separation site including the cholesteric liquid crystal layer may be composed of only the cholesteric liquid crystal layer, or may include other layers such as an alignment layer and a protective layer (additive layer).

(Cholesteric liquid crystal layer)

In this specification, a cholesteric liquid crystal layer means the layer which fixed the cholesteric liquid crystal phase.

It is known that a cholesteric liquid crystal phase exhibits circularly polarized light selective reflection that selectively reflects circularly polarized light of one sense of right circularly polarized light or left circularly polarized light in a specific wavelength range and transmits circularly polarized light of the other sense. have. In the present specification, circularly polarized light selective reflection may be referred to simply as selective reflection.

As a film including a layer on which a cholesteric liquid crystal phase showing circularly polarized light selective reflection is fixed, a film formed of a composition containing a polymerizable liquid crystal compound is known in the art, and for the cholesteric liquid crystal layer, these conventional techniques are described. Reference may be made.

The cholesteric liquid crystal layer should just be a layer in which the orientation of the liquid crystal compound which becomes a cholesteric liquid crystal phase is maintained, and typically, after making a polymeric liquid crystal compound into the aligning state of a cholesteric liquid crystal phase, ultraviolet irradiation, What is necessary is just a layer which superposed | polymerized and hardened | cured by heating, etc., forms the layer with no fluidity, and changed at the same time, and does not produce a change in orientation form by an exterior or external force. In addition, in the cholesteric liquid crystal layer, it is sufficient that the optical properties of the cholesteric liquid crystal phase are maintained in the layer, and the liquid crystal compound in the layer may no longer exhibit liquid crystallinity. For example, a polymeric liquid crystal compound may be high molecular weight by hardening reaction, and may have already lost liquid crystallinity.

The center wavelength λ of the selective reflection of the cholesteric liquid crystal layer depends on the pitch P (= spiral period) of the spiral structure on the cholesteric liquid crystal layer, and the average refractive index n and λ = n of the cholesteric liquid crystal layer Follow the relationship of × P. In addition, in this specification, the center wavelength (lambda) of the selective reflection which a cholesteric liquid crystal layer has has the wavelength in the center position of the reflection peak of the circularly polarized light reflection spectrum measured from the normal line direction of a cholesteric liquid crystal layer. In addition, in this specification, the center wavelength of selective reflection means the center wavelength when measured from the normal line direction of a cholesteric liquid crystal layer.

The selective reflection center wavelength and the half-value width of the cholesteric liquid crystal layer can be obtained as follows.

When the transmission spectrum (measured from the normal direction of the cholesteric liquid crystal layer) of the cholesteric liquid crystal layer is measured using a spectrophotometer UV3150 (Shimazu Seisakusho), a decrease peak of the transmittance can be seen in the selective reflection band. . Of the two wavelengths that become the intermediate (average) transmittances between the minimum transmittance of the peak and the transmittance before the decrease, when the value of the wavelength on the short wavelength side is λ _l (nm) and the value of the wavelength on the long wavelength side is λ _h (nm) , The central wavelength λ of the selective reflection and the half width Δλ can be expressed by the following equation.

λ = (λ _l + λ _h ) / 2

Δλ = (λ _h -λ _l )

The selective reflection center wavelength obtained as described above substantially coincides with the wavelength at the center position of the reflection peak of the circularly polarized light reflection spectrum measured from the normal direction of the cholesteric liquid crystal layer.

As can be seen from the equation of λ = n × P, the center wavelength of the selective reflection can be adjusted by adjusting the pitch of the spiral structure. In the cholesteric liquid crystal layer used for the polarization separation site, among the right circularly polarized light or the left circularly polarized light at the wavelength of selective reflection required for the reflection of light incident from the corresponding organic electroluminescent layer (for example, incident in the normal direction). The center wavelength λ can be adjusted by adjusting the n value and the P value to selectively reflect either side.

That is, in the image display device of the present invention, if the peak (maximum value) of the emission spectrum of the organic electroluminescent layer used is adjusted to be approximately equal to the center wavelength of the selective reflection of the cholesteric liquid crystal layer of the corresponding polarization separation site, do. By matching the wavelength of the emission peak of the organic electroluminescent layer for image display of an image display apparatus with the center wavelength of selective reflection, it reflects the light of one polarization state among the light which an organic electroluminescent layer emitted, and also the other polarization It can transmit light of a state.

In addition, with respect to light incident obliquely to the cholesteric liquid crystal layer, the center wavelength of selective reflection shifts to the short wavelength side. Among the cholesteric liquid crystal layers having a refractive index n ₂ , the central wavelength of selective reflection when a light ray passes at an angle of θ ₂ with respect to the normal direction of the cholesteric liquid crystal layer (the spiral axis direction of the cholesteric liquid crystal layer) is λ _d. Λ _d is represented by the following formula.

λ _d = n ₂ × P × cosθ ₂

The average refractive index n of a cholesteric liquid crystal layer can be adjusted with the kind of polymeric liquid crystal compound, etc.

Since the pitch (P value) of a cholesteric liquid crystal phase depends on the kind of chiral agent used with a polymeric liquid crystal compound, or its addition density | concentration, a desired pitch can be obtained by adjusting these. In addition, the method described in "Introduction to the Liquid Crystal Chemistry Experiment" Japanese Liquid Crystal Society edition Sigma Publication 2007 publication, page 46, and "Liquid Crystal Handbook" liquid crystal manual editorial committee Maruzen page 196 can be used for the method of measuring spiral sense and pitch. .

As a polarization separation part of an image display apparatus, you may use the cholesteric liquid crystal layer which has the center wavelength of selective reflection corresponding to the wavelength of light emission of each organic electroluminescent layer. For example, when the organic electroluminescent layer group includes an organic electroluminescent layer of red luminescence, an organic electroluminescent layer of green luminescence, and an organic electroluminescent layer of blue luminescence, the wavelength range of red light (for example, in a corresponding arrangement) Cholesteric liquid crystal layer having a center wavelength of selective reflection at 580 nm or more and less than 700 nm), a cholesteric liquid crystal layer having a center wavelength of selective reflection at a wavelength range of green light (for example, 500 nm or more and less than 580 nm), What is necessary is just to include the cholesteric liquid crystal layer which has the center wavelength of selective reflection in a wavelength range (for example, 400 nm or more and less than 500 nm).

As each cholesteric liquid crystal layer, the cholesteric liquid crystal layer whose spiral sense is either right or left according to the sense of circularly polarized light which the circularly polarizing plate of the image display apparatus of this invention transmits is used. Specifically, a cholesteric liquid crystal phase that transmits circularly polarized light having the same sense as circularly polarized light transmitted by the circularly polarizing plate is used.

The sense of the reflected circularly polarized light of the cholesteric liquid crystal layer coincides with the sense of the spiral. When multiple types of cholesteric liquid crystal layers are included in the polarization separation layer, the senses of those spirals may all be the same.

(Production method of cholesteric liquid crystal layer)

Hereinafter, the manufacturing method of a cholesteric liquid crystal layer is demonstrated.

The liquid crystal composition containing a polymeric liquid crystal compound is used for formation of a cholesteric liquid crystal layer. The liquid crystal composition may further contain a chiral agent (optical active compound). If necessary, the liquid crystal composition, which is further mixed with a surfactant, a polymerization initiator, or the like and dissolved in a solvent, is applied to a support, an alignment film, a cholesteric liquid crystal layer to be an underlayer, and the like for curing the liquid crystal composition after orientation aging. By immobilization to form a cholesteric liquid crystal layer.

(Polymerizable Liquid Crystal Compound)

Although a rod-shaped liquid crystal compound may be sufficient as a polymeric liquid crystal compound and a disk-shaped liquid crystal compound may be sufficient, a rod-shaped liquid crystal compound is preferable.

A rod-like nematic liquid crystal compound is mentioned as an example of a rod-shaped polymerizable liquid crystal compound. Examples of the rod-like nematic liquid crystal compound include azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano-substituted phenylpyrides. Midines, alkoxy substituted phenylpyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitriles are preferably used. Not only a low molecular liquid crystal compound but a polymeric liquid crystal compound can be used for such a rod-shaped liquid crystal compound.

A polymerizable liquid crystal compound is obtained by introducing a polymerizable group into a liquid crystal compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, an oxetanyl group, and an aziridinyl group, an unsaturated polymerizable group is preferable, and an ethylenically unsaturated polymerizable group is particularly preferable. The polymerizable group can be introduced into the molecules of the liquid crystal compound by various methods. The number of polymerizable groups which the polymerizable liquid crystal compound has is preferably 1 to 6, more preferably 1 to 3. Examples of the polymerizable liquid crystal compound include Makromol. Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Patent No. 4683327, 5622648, 5770107, WO 95/22586, WO95 / 24455, WO97 / 00600, WO98 / 23580, WO98 / 52905, Japanese Patent Laid-Open No. Hei 1-272551, 6-16616, 7-110469, 11-80081, and Japanese Patent Laid-Open. The compound described in Unexamined-Japanese-Patent No. 2001-328973, Unexamined-Japanese-Patent No. 2009-69793, Unexamined-Japanese-Patent No. 2010-113249, Unexamined-Japanese-Patent No. 2011-203636, etc. are contained.

Moreover, as a polymeric liquid crystal compound of that excepting the above, the cyclic organopolysiloxane compound etc. which have a cholesteric liquid crystal phase disclosed in Unexamined-Japanese-Patent No. 57-165480 can be used. Moreover, as the above-mentioned polymer liquid crystal compound, the polymer which introduce | transduced the mesogenic group which shows a liquid crystal in the main chain or the side chain, or both the main chain and the side chain, the polymeric cholesteric liquid crystal which introduce | transduced the cholesteryl group in the side chain, Unexamined-Japanese-Patent No. The liquid crystalline polymer disclosed in JP-A 9-133810, the liquid crystalline polymer disclosed in JP-A-11-293252, and the like can be used.

As the polymerizable liquid crystal compound, it is also preferable to use a liquid crystal compound having two or more kinds of reactive groups having different polymerization conditions in the same molecule. Examples of the combination of reactive groups having different polymerization conditions include a combination of a radical photopolymerizable reactive group and a cationic photopolymerizable reactive group.

It is also preferable to use the liquid crystal compound which shows high refractive index anisotropy (DELTA) n as a polymeric liquid crystal compound. As can be seen from the above formula (Δλ = Δn × P), a wide half-value width Δλ can be obtained by using a liquid crystal compound exhibiting high refractive index anisotropy Δn. For this reason, it is because the wavelength range of the reflection of a polarization separation part can be made wider than the wavelength range of the light emission of an organic electroluminescent layer as mentioned above. Specifically, 0.25 or more are preferable, as for (DELTA) n in 30 degreeC of a liquid crystal compound, 0.3 or more are more preferable, and 0.35 or more are more preferable. Although an upper limit in particular is not restrict | limited, In many cases, it is 0.6 or less.

As a measuring method of refractive index anisotropy (DELTA) n, the method using the wedge-shaped liquid crystal cell of liquid crystal handbook (Liquid Crystal Handbook Editing Committee Edit, Maruzen Co., Ltd.) page 202 is common, and in the case of a compound which is easy to crystallize, It is also possible to estimate the refractive index anisotropy Δn from the extrapolated value by evaluating the mixture.

As a liquid crystal compound which shows high refractive index anisotropy (DELTA) n, For example, US Patent Publication No. 6514578, Japanese Patent Publication 3999400, Japanese Patent Publication 4117832, Japanese Patent Publication 4517416, Japanese Patent Publication 4836335, Japanese Patent Publication 5411770, The compound of Unexamined-Japanese-Patent No. 5411771, 5510321, Unexamined-Japanese-Patent No. 5705465, Unexamined-Japanese-Patent No. 5721484, Unexamined-Japanese-Patent No. 5723641, etc. are mentioned.

As a preferable polymeric liquid crystal compound used in this invention, the compound represented by the following general formula (I) or (II) is mentioned. The compound represented by general formula (I) or (II) shows high refractive index anisotropy Δn.

[Formula 2]

In the formula,

A represents the bivalent aromatic ring group which may have a substituent,

L is a single bond, -C (= O) O-, -OC (= O)-, -NH-C (= O)-, -C (= O) -NH-, -CH = CH-C (= O) O-, and -OC (= O) -CH = CH-, and a linking group selected from the group consisting of

m represents the integer of 2-12,

Sp ¹ and Sp ² each independently represent one or two or more -CH ₂ -in a single bond, a straight or branched alkylene group having 1 to 20 carbon atoms, and a straight or branched alkylene group having 1 to 20 carbon atoms; Consisting of groups substituted with -O-, -S-, -NH-, -N (CH ₃ )-, -C (= 0)-, -OC (= 0)-, or -C (= 0) O- Represents a linking group selected from the group,

Q ¹ and Q ² each independently represent a polymerizable group.

A is a bivalent aromatic ring group which may have a substituent. The divalent aromatic ring group is a group formed by removing two hydrogen atoms from an aromatic ring, and examples of the aromatic ring include benzene, naphthalene, furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine and pyrazine. Etc. can be mentioned. As a bivalent aromatic ring group, a phenylene group is preferable and a 1, 4- phenylene group is especially preferable.

m pieces of A and L may be the same or different.

In the divalent aromatic ring group, the substituent in the case of "having a substituent" is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an amide group, an amino group, and a halogen. And a substituent selected from the group consisting of an atom and a group constituted by combining two or more of the above substituents. In addition, there may be mentioned a substituent represented by the examples of substituent ^{groups, -C (= O) -X 3} -Sp 3 -Q 3. Here, X ³ represents a single bond, -O-, -S-, -NH-, or -N (CH ₃₎ - represents the, Sp ³ and Sp ¹ is a consent, Q ³ represents a polymerizable group. The divalent aromatic ring group may have 1 to 4 substituents. When it has two or more substituents, two or more substituents may mutually be same or different.

In the present specification, the alkyl group may be either linear or branched. 1-30 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, and 1-6 are especially preferable. Examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and neo Pentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, linear or branched heptyl group, octyl group, nonyl group, decyl group, undecyl group, or dodecyl group. The above description of the alkyl group is the same also in the alkoxy group containing the alkyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

In this specification, 3-20 are preferable and, as for carbon number of a cycloalkyl group, 5-10 or less are more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

L is a single bond, -C (= O) O-, -OC (= O)-, -NH-C (= O)-, -C (= O) -NH-, -CH = CH-C (= O) O- and -OC (= O) -CH = CH-. L is preferably -C (= 0) O-, -OC (= 0)-, -NH-C (= 0)-, or -C (= 0) -NH-. m L pieces may be the same or different.

m represents the integer of 2-12, it is preferable that it is 3-7, and it is more preferable that it is 3-5.

Sp ¹ and Sp ² each independently represent a single bond, one or two or more -CH ₂ -in a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms; Consisting of groups substituted with -O-, -S-, -NH-, -N (CH ₃ )-, -C (= 0)-, -OC (= 0)-, or -C (= 0) O- A linking group selected from the group is shown. Sp ¹ and Sp ² are each independently a straight chain having 1 to 10 carbon atoms bonded to a linking group selected from the group consisting of -O-, -OC (= 0)-, and -C (= 0) O- at each end; Composed of one or two or more groups selected from the group consisting of an alkylene group, -OC (= O)-, -C (= O) O-, -O-, and a linear alkylene group having 1 to 10 carbon atoms It is preferable that it is a coupling group, and it is preferable that it is a C1-C10 linear alkylene group which respectively -O- couple | bonded with the both terminal.

Q ¹ and Q ² each independently represent a polymerizable group and preferably represent a polymerizable group selected from the group consisting of groups represented by the following formulas (Q-1) to (Q-5).

[Formula 3]

As a polymerizable group, acryloyl group (formula (Q-1)), methacryloyl group (formula (Q-2)), and oxetanyl group (formula (Q-5)) are preferable. The compound whose both Q <^1> and Q <^2> is an acryloyl group or a methacryloyl group, and either one of Q <^1> and Q <^2> are acryloyl group or a methacryloyl group, and the other is a compound whose oxetanyl group is more preferable Do.

The compound represented by general formula (I) can be synthesize | combined by the method etc. which were described in Unexamined-Japanese-Patent No. 11-513019 (WO97 / 00600).

Although the example of the polymeric compound represented by Formula (I) below is shown, it is not limited to these examples.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

A ¹¹ to A ¹⁴ each independently represent a divalent aromatic carbon group or a divalent heterocyclic group which may have a substituent. The divalent aromatic carbon group is a group formed by removing two hydrogen atoms from an aromatic carbocyclic ring, and the divalent heterocyclic group is a group formed by removing two hydrogen atoms from a heterocycle. As an aromatic carbocyclic ring, a benzene ring and a naphthalene ring are mentioned. As a heterocyclic ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazoline Dean ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, cyine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring , Pyrimidine ring, pyrazine ring, piperazine ring, and triazine ring. Especially, it is preferable that A <^11> -A <^14> is a divalent aromatic carbon group, It is more preferable that it is a phenylene group, It is more preferable that it is a 1, 4- phenylene group.

The kind of substituent which may be substituted by an aromatic carbon group or a heterocyclic group is not specifically limited, For example, a halogen atom, a cyano group, a nitro group, an alkyl group, a halogen substituted alkyl group, an alkoxy group, an alkylthio group, acyl An oxy group, an alkoxycarbonyl group, a carbamoyl group, an alkyl substituted carbamoyl group, and the C2-C6 acylamino group are mentioned.

X ¹¹ and X ¹² are each independently a single bond, -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH- or -C≡C- is represented. Especially, a single bond, -COO-, -CONH-, -NHCO-, or -C≡C- is preferable.

Y ¹¹ and Y ¹² are each independently a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, or -C≡C- is represented. Especially, -O- is preferable.

Sp ¹¹ and Sp ¹² each independently represent a single bond or an alkylene group having 1 to 25 carbon atoms. The alkylene group may be any of linear, branched, and cyclic. Especially, a C1-C10 alkylene group is more preferable.

Q ¹¹ and Q ¹² each independently represent a hydrogen atom or a polymerizable group, and at least one of Q ¹¹ and Q ¹² represents a polymerizable group. As a polymeric group, the polymeric group selected from the group which consists of groups represented by Formula (Q-1)-a formula (Q-5) is illustrated. As a polymeric group represented by P <^1> or P <^2> , acryloyl group (formula (Q-1)) and methacryloyl group (formula (Q-2)) are preferable.

n <^11> and n <^12> represent the integer of 0-2 each independently, and when n <^11> or n <^12> is 2, two or more A <^11> , A <^2> , X <^11> and X <^12> may be same or different.

As a specific example of a compound represented by general formula (II), the compound shown by following formula (2-1)-(2-30) is mentioned.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

You may use together 2 or more types of polymeric liquid crystal compounds. When two or more types of polymerizable liquid crystal compounds are used together, orientation temperature can be reduced.

Moreover, when using together the liquid crystal compound which has two or more types of reactive groups with different polymerization conditions in the same molecule, and the liquid crystal compound which has two or more reactive groups with the same polymerization conditions in the same molecule, the reflection band of selective reflection can be expanded, and it is more preferable. Do. Specifically, the combination of the liquid crystal compound containing a (meth) acryloyl group and an oxetanyl group, and the liquid crystal compound containing two (meth) acryloyl groups is mentioned.

It is preferable that it is 80-99.9 mass% with respect to solid content mass (mass except a solvent) of a liquid crystal composition, and, as for the addition amount of the polymeric liquid crystal compound in a liquid crystal composition, it is more preferable that it is 85-99.5 mass%, and 90-99 mass Particularly preferred is%.

(Chiral agent: optically active compound)

It is preferable that the material used for formation of a cholesteric liquid crystal layer contains the chiral agent. The chiral agent has a function of causing a helical structure of the cholesteric liquid crystal phase. The chiral compound may be selected according to the purpose because the sense or spiral pitch of the spiral caused by the compound is different.

There is no restriction | limiting in particular as a chiral agent, A well-known compound can be used. Examples of chiral agents include liquid crystal device handbooks (Chapter 3, paragraphs 4-3, chiral agents for TN and STN, p. 199, Japanese Society of Research Promotion Association 142 Committee, 1989), Japanese Unexamined Patent Publication No. 2003-287623, Japan The compound described in each of Unexamined-Japanese-Patent No. 2002-302487, Unexamined-Japanese-Patent No. 2002-80478, Unexamined-Japanese-Patent No. 2002-80851, Unexamined-Japanese-Patent No. 2010-181852, or Unexamined-Japanese-Patent No. 2014-034581 is mentioned. Can be.

Although a chiral agent generally contains a subsidiary carbon atom, a layered subsidiary compound or a surface subsidiary compound containing no subsidiary carbon atoms may also be used as the chiral agent. Examples of the layered subtitle compound or the cotton subtitle compound include binaphthyl, helicene, paracyclohexane and derivatives thereof. The chiral agent may have a polymerizable group. When both a chiral agent and a liquid crystal compound have a polymeric group, the repeating unit guide | induced from a polymeric liquid crystal compound and the repeating unit guide | induced from a chiral agent by the polymerization reaction of a polymeric chiral agent and a polymeric liquid crystal compound It is possible to form a polymer having. In this aspect, it is preferable that the polymeric group which a polymeric chiral agent has is the group of the same kind as the polymeric group which a polymeric liquid crystal compound has. Therefore, it is preferable that a polymerizable group of a chiral agent is an unsaturated polymerizable group, an epoxy group, or an aziridinyl group, It is more preferable that it is an unsaturated polymerizable group, It is especially preferable that it is an ethylenically unsaturated polymerizable group.

Moreover, a chiral agent may be a liquid crystal compound.

As a chiral agent, an isosorbide derivative, an isomannide derivative, or a binaphthyl derivative can be used preferably. As an iso carbide derivative, you may use commercial items, such as LC-756 by BASF Corporation.

0.01 mol%-200 mol% are preferable with respect to the total molar amount of a polymeric liquid crystal compound, and, as for content of a chiral agent in a liquid crystal composition, 1 mol%-30 mol% are more preferable.

(Polymerization initiator)

It is preferable that a liquid crystal composition contains the polymerization initiator. In the aspect which advances a polymerization reaction by ultraviolet irradiation, it is preferable that the polymerization initiator to be used is a photoinitiator which can start a polymerization reaction by ultraviolet irradiation. As an example of a photoinitiator, a radical polymerization initiator and a cationic polymerization initiator are mentioned.

Examples of the radical polymerization initiators include α-carbonyl compounds (described in the specifications of US Patent No. 2366766 and 2367670), Acyloinether (described in US Patent No. 2448828), and α-hydrocarbon substituted aromatic acyl A loin compound (described in US Patent Publication No. 2722512), a multinuclear quinone compound (described in each specification of US Patent Publication No. 3046127, 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (US Patent Publication) 3549367), acridine and phenazine compounds (Japanese Laid-Open Patent Publication No. 60-105667, US Patent No. 4239850), Acylphosphine oxide compound (Japanese Laid-Open Patent Publication No. 63-40799, Japan Japanese Patent Application Laid-open No. Hei 5-29234, Japanese Patent Application Laid-open No. Hei 10-95788, Japanese Patent Application Laid-open No. Hei 10-29997, Japanese Patent Application Laid-Open No. 2001-233842, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Laid-Open Publication 2006-342166, Japanese Laid-Open Patent Publication 2 013-114249, Japanese Unexamined Patent Publication No. 2014-137466, Japanese Patent No. 4223071, Japanese Unexamined Patent Publication No. 2010-262028, Japanese Unexamined Patent Publication No. 2014-500852), Oxime compound (Japanese Unexamined Patent Publication No. 2000-66385) Japanese Patent Publication No. 4454067), an oxadiazole compound (described in US Patent No. 4212970), and the like. For example, Paragraph 0500 of Unexamined-Japanese-Patent No. 2012-208494-description of 0475 can also be referred.

As a radical polymerization initiator, it is preferable to use an acyl phosphine oxide compound or an oxime compound.

As an acylphosphine oxide compound, IRGACURE 819 (compound name: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) by BASF Japan Co., Ltd. which is a commercial item can be used, for example. As an oxime compound, IRGACURE OXE01 (made by BASF Corporation), IRGACURE OXE02 (made by BASF Corporation), TR-PBG-304 (made by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka a Commercially available products, such as Kles NCI-831, Adeka Ackles NCI-930 (manufactured by ADEKA), and Adeka Ackles NCI-831 (manufactured by ADEKA) can be used.

As a cationic polymerization initiator, an organic sulfonium salt type, an iodonium salt type, a phosphonium salt type, etc. can be illustrated, An organic sulfonium salt type is preferable, and a triphenyl sulfonium salt is especially preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.

1 type of polymerization initiators may be used and may use 2 or more types together.

It is preferable that it is 0.1-20 mass% with respect to content of a polymeric liquid crystal compound, and, as for content of the photoinitiator in a liquid crystal composition, it is more preferable that it is 0.5 mass%-5 mass%.

(Bridge)

The liquid crystal composition may optionally contain a crosslinking agent for improving film strength after curing and improving durability. As a crosslinking agent, what is hardened | cured by ultraviolet-ray, heat, moisture, etc. can be used suitably.

There is no restriction | limiting in particular as a crosslinking agent, According to the objective, it can select suitably, For example, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate Polyfunctional acrylate compounds such as these; Epoxy compounds such as glycidyl (meth) acrylate and ethylene glycol diglycidyl ether; Aziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] and 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; Isocyanate compounds such as hexamethylene diisocyanate and biuret isocyanate; Poly oxazoline compound which has an oxazoline group in a side chain; Alkoxysilane compounds, such as vinyl trimethoxysilane and N- (2-aminoethyl) 3-aminopropyl trimethoxysilane, etc. are mentioned. Among these, a polyfunctional acrylate compound is preferable. As a polyfunctional acrylate compound, a 3-6 functional acrylate compound is preferable and a 4-6 functional acrylate compound is more preferable. Moreover, a well-known catalyst can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to improving membrane strength and durability. These may be used individually by 1 type and may use 2 or more types together.

As for content of the crosslinking agent in a liquid crystal composition, 0 mass part-8.0 mass parts are preferable with respect to 100 mass parts of polymerizable liquid crystal compounds in a liquid crystal composition, 0.1 mass part-7.0 mass parts are more preferable, 0.2 mass part-5.5 mass parts further desirable.

(Orientation control agent)

In a liquid crystal composition, you may add the orientation controlling agent which contributes in order to planner orientation stably or quickly. As an example of an orientation control agent, the fluorine (meth) acrylate type polymer described in Unexamined-Japanese-Patent No. 2007-272185, etc., and Paragraph [0031]-[0034] etc. of Unexamined-Japanese-Patent No. 2012-203237 etc. are described. The compound etc. which are represented by Formula (I)-(IV) are mentioned.

In addition, as an orientation control agent, you may use individually by 1 type, and may use 2 or more types together.

0.01 mass%-10 mass% are preferable with respect to the total mass of a polymeric liquid crystal compound, as for the addition amount of the orientation control agent in a liquid crystal composition, 0.01 mass%-5.0 mass% are more preferable, 0.02 mass%-1.0 Mass% is particularly preferred.

(Other additives)

In addition, the liquid crystal composition may contain at least one selected from various additives such as a surfactant for adjusting the surface tension of the coating film and making the thickness uniform, and a polymerizable compound. Moreover, in a liquid crystal composition, a polymerization inhibitor, antioxidant, an ultraviolet absorber, a light stabilizer, a coloring material, metal oxide fine particles, etc. can be added further in the range which does not reduce optical performance as needed.

(menstruum)

There is no restriction | limiting in particular as a solvent used for preparation of a liquid crystal composition, Although it can select suitably according to the objective, The organic solvent is used preferably.

There is no restriction | limiting in particular as an organic solvent, According to the objective, it can select suitably, For example, ketones, alkyl halides, amides, sulfoxides, heterocyclic compound, hydrocarbons, esters, ethers, etc. are mentioned. have. These may be used individually by 1 type and may use 2 or more types together. Among these, ketones are particularly preferable when considering the load on the environment.

(Application, orientation, polymerization)

There is no restriction | limiting in particular and the coating method of the liquid crystal composition to a support body, an oriented film, a quarter wave plate, a cholesteric liquid crystal layer used as an underlayer, can be suitably selected according to the objective, For example, a wire bar coating method, a curtain Coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, spin coating method, dip coating method, spray coating method, slide coating method and the like. Moreover, it can also carry out by transferring the liquid crystal composition coated on the support body separately. Liquid crystal molecules are oriented by heating the coated liquid crystal composition. What is necessary is just to perform cholesteric orientation at the time of cholesteric liquid crystal layer formation, and it is preferable to carry out nematic orientation at the time of quarter wave plate formation. In cholesteric orientation, 200 degrees C or less is preferable, and, as for heating temperature, 130 degrees C or less is more preferable. By this alignment process, the optical thin film which twist-aligned so that a polymeric liquid crystal compound may have a spiral axis in the direction substantially perpendicular to a film surface can be obtained. 50 degreeC-120 degreeC is preferable, and, as for a nematic orientation, 60 degreeC-100 degreeC is more preferable.

The oriented liquid crystal compound can further superpose | polymerize and can harden a liquid crystal composition. Although superposition | polymerization may be any of photopolymerization using thermal polymerization and light irradiation, photopolymerization is preferable. It is preferable to use ultraviolet-ray for light irradiation. The irradiation energy is, the ^{20mJ / cm 2 ~ 50J / cm} 2 are preferred, and more preferably ^{100mJ / cm 2 ~ 1,500mJ / cm} 2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions or under a nitrogen atmosphere. The irradiation ultraviolet wavelength is preferably 350 nm to 430 nm. It is preferable that a polymerization reaction rate is high from a viewpoint of stability, 70% or more is preferable and 80% or more is more preferable. A polymerization reaction rate can be determined by measuring the consumption ratio of a polymeric functional group using IR absorption spectrum.

Although the thickness of each cholesteric liquid crystal layer will not be specifically limited if it is a range which shows the said characteristic, Preferably it is the range of 1.0 micrometer or more and 20 micrometers or less, More preferably, it is the range of 2.0 micrometers or more and 10 micrometers or less.

(Support)

The liquid crystal composition may be applied to the surface of the alignment layer formed on the surface of the support or the support to form a layer. The support or the support and the alignment layer may be peeled off after layer formation. For example, you may peel a layer after sticking to a light emitting element substrate. As an example of a support body, cellulose derivatives, such as triacetyl cellulose, an acrylic resin, a cycloolefin polymer, a glass plate, etc. are mentioned.

The thickness of the support may be about 5 µm to 1000 µm, preferably 10 µm to 250 µm, and more preferably 15 µm to 120 µm.

(Orientation layer)

When forming a cholesteric liquid crystal layer, it is preferable to regulate the orientation state of a liquid crystal composition in the orientation layer provided directly on or on a support body. As long as an orientation layer can provide orientation to an optically anisotropic layer, what kind of layer may be sufficient. Preferred examples of the alignment layer include layers in which organic compounds such as polymers (resin such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, polyetherimide, polyamide, modified polyamide, etc.) are rubbed. , A photoalignment layer expressing the orientation of liquid crystals by polarized light irradiation represented by an azobenzene polymer or a cinnamate polymer, an evaporated layer of an inorganic compound, and a layer having microgrooves, and further? -Triicosanic acid, die A cumulative film formed by a Langmuir blob method (LB film) such as octadecyl methylammonium chloride and methyl stearyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field. As an orientation layer, in the aspect of rubbing, it is preferable to contain polyvinyl alcohol, and it is especially preferable that it can bridge | crosslink with at least one layer above or below an orientation layer. Specifically, the alignment layers described in JP-A-2009-69793, JP-A-2010-113249, and JP-A-2011-203636 can be used. Moreover, a photo-alignment layer can also be used suitably. This is because when the optical alignment layer is used, the generation of alignment defects due to the micro foreign matter can be suppressed, and even a fine shape can form a cholesteric liquid crystal layer with high optical performance. For example, the liquid crystal aligning agent (for example, the liquid crystal aligning agent containing an epoxy containing polyorganosiloxane) of Unexamined-Japanese-Patent No. 2015-26050 can be used. In order to fully exhibit the orientation regulation force of an orientation layer, you may perform the process (orientation process) which controls the temperature of the apply | coated liquid crystal composition and expresses a desired phase.

It is preferable that it is 0.01 micrometer-5.0 micrometers, and, as for the thickness of an orientation layer, it is more preferable that it is 0.05 micrometer-2.0 micrometers.

(Patterning method)

A cholesteric liquid crystal layer can be formed by patterning in order to form the polarization separation layer containing a plurality of types of polarization separation sites showing polarization separation at different wavelengths. By using the cholesteric liquid crystal layer of the pattern shape which adjusted the selective reflection wavelength corresponding to the light emission wavelength of each organic electroluminescent layer of a light emitting element substrate, light utilization efficiency can be improved more. By forming a cholesteric liquid crystal layer by a patterning method, formation of the polarization separation site | part and visible light transmission region in a polarization separation layer, and formation of the polarization separation site arrange | positioned in matrix form can also be performed.

As the patterning method, a method by solvent development or a method of using a photoisomerized chiral agent (Japanese Patent Laid-Open No. 2001-159706), a method of orientation-fixing in advance and transferring the cholesteric liquid crystal layer using a laser or a thermal head (Japanese Unexamined Patent Application Publication No. 2001-4822, Japanese Unexamined Patent Application Publication No. 2001-4824), inkjet method (Japanese Unexamined Patent Application Publication No. 2001-159709), and a method of using temperature dependence of the spiral pitch of cholesteric 2001-159708), and the method of changing the amount of ultraviolet irradiation at the time of hardening of a liquid crystal composition stepwise between regions, etc. are mentioned.

As an example, the method of using a photoisomerization chiral agent can be performed as follows. Using the liquid crystal composition containing a photoisomerization chiral agent, first, the cholesteric liquid crystal layer which has the central wavelength of selective reflection in an ultraviolet wavelength range is formed in the whole surface. Thereafter, a portion of the cholesteric liquid crystal layer is fixed in a state having a central wavelength of selective reflection in the ultraviolet wavelength range or the infrared wavelength range by pattern exposure (ultraviolet irradiation) to form a visible light transmission region. Subsequently, light of the absorption wavelength of the chiral agent is selectively irradiated to each region with an appropriate amount of light according to each region having the central wavelength of selective reflection to be formed. Thereby, the chiral agent is isomerized and the pitch of the spiral structure along each area is obtained. Finally, the entire surface is irradiated with ultraviolet rays to fix the orientation of each region, and a polarization splitting layer having a pattern of a cholesteric liquid crystal layer having a visible light transmitting region in one layer and a central wavelength of selective reflection in a desired wavelength range. Can be formed.

In the patterning method, pattern exposure can be performed as mentioned above.

As a method of pattern exposure, the contact exposure using a mask, proxy exposure, projection exposure, etc. are mentioned. As irradiation wavelength of the light source of the said exposure, it is preferable to have a peak at 250-450 nm, and it is more preferable to have a peak at 300-410 nm. Specifically, an ultra high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a blue laser, etc. are mentioned. The preferred exposure dose as normal and 3 ~ 2000mJ / cm ² or so, more preferably 5 ~ 1000mJ / cm ² or so, more preferably 10 ~ 500mJ / cm ² or so, and most preferably 10 ~ 100mJ / cm ² or so.

Depending on the material to be used, you may perform pattern heating instead of pattern exposure. As a method of pattern heating, the contact heating using the heated patterning plate, the heating by an infrared laser, etc. can be used.

In addition, you may combine both.

By using pattern exposure, a polarization splitting layer composed of a plurality of layers may be formed as follows.

That is, after pattern exposure is performed on the layer formed of the first liquid crystal composition, pattern exposure is performed on the layer formed of the first liquid crystal composition, and then a layer formed of a new second liquid crystal composition is formed or transferred thereon, followed by another pattern. Exposure can be performed. Moreover, the layer formed from the new 3rd liquid crystal composition can be formed or transferred on it, and another pattern exposure can be performed after that.

The first liquid crystal composition, the second liquid crystal composition, and the third liquid crystal composition may be derived from the same composition or may be derived from another composition. It is also preferable to use three kinds of liquid crystal compositions differing only in the concentration of the chiral agent.

The unexposed part can be optically isotropic by heating at 50 degreeC or more and 400 degrees C or less, Preferably it is 80 degreeC or more and 200 degrees C or less with respect to the layer of the pattern exposed liquid crystal composition. By doing in this way, the layer which has a cholesteric liquid crystal layer can be formed in a pattern shape. An optically isotropic region may be formed so as to distinguish the polarization separation site and may be a visible light transmitting region. A cholesteric liquid crystal layer having a central wavelength of selective reflection in a wavelength range of red light, a cholesteric liquid crystal layer having a central wavelength of selective reflection in a wavelength range of green light, and a central wavelength of selective reflection in a wavelength range of blue light With respect to the cholesteric liquid crystal layer, a polarizing separation layer is formed by forming layers having cholesteric liquid crystal layers in a pattern shape, respectively, so as to have a wavelength range corresponding to the color of the organic electroluminescent layer of the light emitting element substrate, and laminating them in plurality. Can be formed.

About pattern exposure and formation of the pattern-shaped cholesteric liquid crystal layer (optical anisotropic layer), it is described in Unexamined-Japanese-Patent No. 2009-69793, Unexamined-Japanese-Patent No. 2010-113249, and Unexamined-Japanese-Patent No. 2011-203636. See.

(Protective layer (additive layer))

In particular, when forming the polarization separation layer which has a polarization separation site in a pattern shape using a liquid crystal composition, you may use a protective layer. The protective layer should just contain at least 1 sort (s) of polymerization initiator which has a function which starts the polymerization reaction by the unreacted reactive group which remain | survives after temporarily hardening a liquid crystal composition. It is preferable that the cholesteric liquid crystal layer and the protective layer directly contact each other. Although there is no limitation in particular as a structure of the protective layer containing a polymerization initiator, It is preferable to contain at least 1 sort (s) of polymer other than a polymerization initiator.

Although there is no limitation in particular as a polymer (it may be called "binder" as an alias in this invention), The copolymer of polymethyl (meth) acrylate, (meth) acrylic acid, and various esters thereof, polystyrene, styrene, and (meth Copolymers of acrylic acid or various (meth) acrylic acid esters, polyvinyl toluene, vinyl toluene and copolymers of (meth) acrylic acid or various (meth) acrylic acid esters, styrene / vinyl toluene copolymers, polyvinyl chloride, polyvinyl chloride Nilidene, polyvinyl acetate, vinyl acetate / ethylene copolymer, vinyl acetate / vinyl chloride copolymer, polyester, polyimide, carboxymethylcellulose, polyethylene, polypropylene, polycarbonate, and the like. Preferred examples include copolymers of methyl (meth) acrylate and (meth) acrylic acid, copolymers of allyl (meth) acrylate and (meth) acrylic acid, and multi-part copolymers of benzyl (meth) acrylate and (meth) acrylic acid and other monomers. Etc. can be mentioned. These polymers may be used independently or may be used in combination of multiple types. 20-99 mass% is common, as for content of the polymer with respect to a total solid, 40-99 mass% is preferable, and 60-98 mass% is more preferable.

(Production method of polarization separation layer)

What is necessary is just to produce the polarization separation site | part containing a cholesteric liquid crystal layer to the said support body surface, the retardation layer surface, the circularly polarizing plate surface, etc. The obtained laminated body can be used as a film containing an optical functional layer as it is.

Circular Polarizer

The circular polarizing plate is provided on the image display side of the organic electroluminescent layer in order to reduce the surface reflection of external light and improve the contrast in the organic EL image display device. As the circular polarizing plate, a known circular polarizing plate can be used as the circular polarizing plate used in the organic EL image display device.

The circular polarizing plate includes a phase difference layer and a polarizing layer. The circular polarizing plate may have other layers such as an adhesive layer and a surface protective layer. In the image display device of the present invention, the circularly polarizing plate is disposed so that the polarization separating layer, the retardation layer, and the polarizing layer are in this order. The circular polarizing plate may consist of a retardation layer and a polarizing layer. It is preferable that a phase difference layer consists of a quarter wave plate, and it is preferable that a polarizing layer consists of a linear polarizing plate.

The linearly polarizing plate transmits a specific linearly polarized light among the light passing therethrough, and absorbs the linearly polarized light which is orthogonal to this. As a linear polarizing plate, for example, polyvinyl alcohol is absorbed and stretched by iodine, and a protective layer of triacetylcellulose is provided on both surfaces of the film to which the polarizing function is provided, or metal nanorods such as Ag are added to polyvinyl alcohol. And the like can be used.

The quarter wave plate may be a retardation layer functioning as a quarter wave plate in the visible light region. As an example of a quarter wave plate, the broadband 1/4 wave plate etc. which laminated | stacked a one-layered quarter wave plate, a quarter wave plate, and a 1/2 wave phase difference plate are mentioned, It can use suitably.

In the present specification, the phase difference means frontal retardation. Retardation can be measured using the polarization retardation analyzer AxoScan by AXOMETRICS.

There is no restriction | limiting in particular as a quarter wave plate, According to the objective, it can select suitably. For example, a quartz film, an elongated polycarbonate film, an elongated norbornene-based polymer film, a transparent film orientated by containing birefringent inorganic particles such as strontium carbonate, a thin film in which an inorganic dielectric is obliquely deposited on a support, or The liquid crystal composition is apply | coated to a support body or an oriented film, and the polymerizable liquid crystal compound in a liquid crystal composition is formed in nematic orientation in a liquid crystal state, and the thing formed by fixing by optical crosslinking and thermal crosslinking therefrom, etc. are mentioned here. You may use what combined these multiple.

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, reagents, amounts of substances, proportions thereof, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following Examples.

<Example 1>

(Preparation of orientation film composition A)

The composition shown below was stirred and dissolved in the container kept at 80 degreeC, and the alignment film composition A was prepared.

-------------------------------------------------- -----------

Alignment film composition A (mass part)

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Pure 97.2

PVA-205 (gure product) 2.8

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(Preparation of composition LC-1 for polarization separation layers)

The following composition was prepared, and it filtered with the polypropylene filter of 0.2 micrometer of pore diameters, and used as composition LC-1 for polarization separation layers.

LC-1-1 was synthesize | combined based on the method of Unexamined-Japanese-Patent No. 2004-12382. LC-1-1 is a liquid crystal compound which has two reactive groups, the other of two reactive groups is an acryl group which is a radical reactive group, and the other is an oxetane group which is a cationic reactive group. LC-1-2 was synthesized according to the method described in Tetrahedron Lett., Vol. 43, page 6793 (202).

-------------------------------------------------- -----------

Composition LC-1 (parts by mass) for polarization separation layer

-------------------------------------------------- -----------

Rod-shaped liquid crystal (LC-1-1) 19.57

Horizontal Alignment Agent (LC-1-2) 0.01

Cationic monomer (OXT-121, manufactured by Toagosei Co., Ltd.) 0.98

Cationic initiator

(Curacure UVI6974, product made by Dow Chemical) 0.4

Polymerization controlling agent (IRGANOX1076, made by BASF) 0.02

Methyl ethyl ketone 80.0

-------------------------------------------------- ----------

[Formula 14]

-------------------------------------------------- ----------

Protective layer composition AD-1 (mass part)

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Benzyl methacrylate / methacrylic acid / methyl methacrylate

35.9 / 22.4 / 41.7 molar ratio random copolymer

(Weight average molecular weight 3.8 million) 8.05

Radical Polymerization Initiator (2-Trichloromethyl-5- (p-styrylstyryl) 1,3,4-oxadiazole) 0.12

Hydroquinone Monomethyl Ether 0.002

Mega pack F-554 (product made by DIC Corporation) 0.05

Propylene Glycol Monomethyl Ether Acetate 34.80

Methyl ethyl ketone 50.5

Methanol 1.61

-------------------------------------------------- ---------

(Formation of patterned polarization separation layer)

After uniformly apply | coating the oriented-film composition A prepared above on the roll-shaped TAC film of 60 micrometers in thickness and 30 cm in width using a slit coater, it dries for 2 minutes in 100 degreeC oven, and it has an orientation film with a film thickness of 0.5 micrometer. TAC film was obtained. The rubbing process was performed to this orientation film in the direction parallel to an application | coating direction. The composition LC-1 for polarizing separation layers was applied onto a rubbing treatment surface. Subsequently, heat-aging is carried out for 60 second at the membrane surface temperature of 80 degreeC, and immediately after that, it irradiates the ultraviolet-ray of 500mJ / cm <^2> using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under 70 degreeC air of membrane surface, By fixing an orientation state, the manufacturing material for polarization separation layers was formed.

The protective layer composition AD-1 prepared above was apply | coated on the said manufacturing material for polarization separation layers, and after drying for 80 degreeC and 60 second, PLA-501F exposure machine (Ultra-high pressure mercury lamp) by Canon Corporation in 25 degreeC air. It exposed using the mask at the exposure amount of 50mJ / cm <^2> through the mask.

As the mask, a quartz mask having a patterned area having a light transmitting portion (white display portion) at a distance shown in FIG. 1 having 25 cm x 15 cm was used. The light shielding portion (parts other than the white marking portion) of the mask is Cr. In addition, arrangement | positioning of the light transmitting part of a mask corresponds to arrangement | positioning of the organic electroluminescent layer in a light emitting element substrate. The interval in the MD (Machine direction) direction (the major axis direction of the material) of the light transmitting portion of the mask was 99.9 on average with respect to the interval of the organic electroluminescent layer in consideration of 0.1%, which is the elongation in the MD direction used in the bonding process of the light emitting device substrate. To be%.

Thereafter, the whole substrate is baked in an oven at 140 ° C. for 30 minutes, so that the film having the polarization separation layer in which the polarization separation site having the central wavelength of selective reflection in the blue region is arranged in a matrix in an optically isotropic region. Got it.

(Production of Transfer Film with Adhesive Layer)

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Composition (mass part) of coating liquid H-1 for forming an adhesive layer

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Methanol 11.1

Propylene Glycol Monomethyl Ether Acetate 6.36

Methyl ethyl ketone 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.) 5.83

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37,

Weight average molecular weight = 10,000, Tg ≒ 100 ° C) 13.6

Polymerizable compound brand name: BPE-500 (manufactured by Shin-Nakamura Chemical Industries, Ltd.) 9.1

Mega pack F-554 (product made by DIC Corporation) 0.54

Thermal polymerization initiator AIBN (made by Wako Junyaku, decomposition temperature 100-103 degrees Celsius) 0.2

-------------------------------------------------- ---------------------

The coating solution H-1 was applied onto a roll-shaped PET film having a thickness of 75 μm and a width of 30 cm, which was a supporting member, and dried at 60 ° C. for 2 minutes to prepare a transfer film with an adhesive layer. The thickness of the adhesive layer adjusted the coating amount to 10 μm.

(Adhesion to the light emitting element substrate)

On a barrier layer of a top emission type light emitting element substrate having a length of about 27 cm, a width of about 15 cm, and an organic electroluminescent layer having a pitch of 57.74 µm, a transfer film with an adhesive layer produced by the above method was manufactured by Laminator (Hitachi Industries, Ltd.). (Lamic II type)). The conditions are as follows.

Web Tension 86.4N

Substrate Preheating Temperature 80 ℃

Rubber roller temperature 80 ℃

Linear pressure 50N / cm

Conveying speed 3.0m / min

Subsequently, the PET film serving as the branch was peeled off, and only the adhesive layer was transferred onto the light emitting element substrate.

The organic electroluminescent layer is overlapped with the light emitting element substrate to which the adhesive layer was transferred, and the TAC film in which the polarizing separation layer was formed so as to face the adhesive layer and the surface of the polarization separating layer so as to face the width direction of the film and the longitudinal direction of the light emitting element substrate. The organic electroluminescent layer and the polarization separation site were aligned with each other while the tension was kept constant so that the polarization separation site and the polarization separation site were overlapped, and were bonded by a laminator. Fine adjustment of the relative position of the light emitting element substrate and the material for preparation for polarization separation layers was repeated, and the sample was produced, observing the relative position of the organic electroluminescent layer and the polarization separation site after bonding each time under a microscope. The conditions of laminating were as follows, and the elongation of the TAC film at this time was 0.1%.

Web Tension 86.4N

Substrate Preheating Temperature 80 ℃

Rubber roller temperature 80 ℃

Linear pressure 50N / cm

Conveying speed 3.0m / min

Immediately after bonding, the light emitting element substrate and the optical film were heated at 103 degreeC, maintaining the web tension, and the adhesive layer was thermosetted. Heating was performed using the preheating by infrared rays, and the setting conditions were adjusted, confirming by thermocouple that the temperature of a contact bonding layer rises to 103 degreeC.

Then, the extra optical film which protruded rather than the light emitting element substrate was cut | disconnected, and the light emitting element substrate with an optical film was produced.

<Example 2>

Instead of the coating liquid H-1 for forming the adhesive layer, the coating liquid H-2 for forming the adhesive layer was used, and, except that the curing method of the adhesive layer after bonding was changed as follows, the same method as in Example 1 was performed. The light emitting element substrate with an optical film was produced.

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Composition (mass part) of coating liquid H-2 for forming an adhesive layer

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Methanol 11.1

Propylene Glycol Monomethyl Ether Acetate 6.36

Methyl ethyl ketone 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.) 5.83

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C) 13.6

Polymerizable compound brand name: BPE-500 (manufactured by Shin-Nakamura Chemical Industries, Ltd.) 9.1

Mega pack F-554 (product made in DIC) 0.54

Photoinitiator Irgacure 907 (made by BASF Corporation) 0.2

-------------------------------------------------- ---------------------

The said coating liquid H-2 was apply | coated on the roll-shaped PET film of thickness 75micrometer which is a support body, and it dried at 60 degreeC for 2 minutes, and produced the transfer film with an adhesive layer. The thickness of the adhesive layer adjusted the coating amount to 10 μm.

After bonding in the same procedure as in Example 1, 1000 mJ / cm ² (365 nm) of ultraviolet rays were irradiated onto the light emitting element substrate and the optical film from the optical film side while maintaining the web tension, and the adhesive layer was photocured.

<Example 3>

The thickness of the TAC film used for the optical film was 30 micrometers, and it carried out similarly to Example 2 except having adjusted the web tension at the time of bonding a light emitting element substrate and an optical film to 43N, and bonding. The light emitting element substrate of the optical film part was produced. The elongation of an optical film at the time of sticking an optical film to a light emitting element substrate was 1%.

<Example 4>

Except having made the thickness of the contact bonding layer into 2 micrometers, it carried out similarly to Example 2, and produced the light emitting element substrate with an optical film of Example 4.

Example 5

A light emitting element substrate with an optical film of Example 5 was produced in the same manner as in Example 2, except that the thickness of the adhesive layer was 30 μm.

<Example 6>

The light emitting element substrate with an optical film of Example 6 was produced in the same manner as in Example 2 except that the following coating liquid H-3 for forming an adhesive layer was used instead of the coating liquid H-2 for forming an adhesive layer. .

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Composition (mass part) of coating liquid H-3 for forming an adhesive layer

-------------------------------------------------- ---------------------

Methanol 11.1

Propylene Glycol Monomethyl Ether Acetate 6.36

Methyl ethyl ketone 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 40,000, Tg ≒ 70 ° C.) 5.83

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C) 13.6

Polymerizable compound brand name: BPE-500 (manufactured by Shin-Nakamura Chemical Industries, Ltd.) 9.1

Mega pack F-554 (product made in DIC) 0.54

Photoinitiator Irgacure 907 (made by BASF Corporation) 0.2

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<Example 7>

The light emitting element substrate with an optical film of Example 7 was produced in the same manner as in Example 2 except that the following composition H-4 was used instead of the coating liquid H-2 for forming an adhesive layer.

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Composition (mass part) of coating liquid H-4 for forming an adhesive layer

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Methanol 11.1

Propylene Glycol Monomethyl Ether Acetate 6.36

Methyl ethyl ketone 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 600,000, Tg ≒ 70 ° C.) 5.83

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C) 13.6

Polymerizable compound brand name: BPE-500 (manufactured by Shin-Nakamura Chemical Industries, Ltd.) 9.1

Mega pack F-554 (product made in DIC) 0.54

Photoinitiator Irgacure 907 (made by BASF Corporation) 0.2

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Comparative Example 1

A light emitting element substrate with an optical film was produced in the same manner as in Example 2, except that the coating liquid H-5 for forming an adhesive layer was used instead of the coating liquid H-2 for forming an adhesive layer.

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Composition (mass part) of coating liquid H-5 for forming an adhesive layer

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Methanol 11.1

Propylene Glycol Monomethyl Ether Acetate 6.36

Methyl ethyl ketone 52.4

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.) 5.83

Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg ≒ 100 ° C) 13.6

Polymerizable compound brand name: BPE-500 (manufactured by Shin-Nakamura Chemical Industries, Ltd.) 9.1

Mega pack F-554 (product made by DIC Corporation) 0.54

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[evaluation]

The produced light emitting element substrate with an optical film was observed under a microscope, and the average value of the value of the shift | offset | difference of the center of the polarization separation site and the center of the organic electroluminescent layer in nine places was evaluated within the board | substrate surface.

The light emitting element substrate with a produced optical film was made to emit light, and it measured how much the brightness | luminance of an organic electroluminescent image display apparatus is improving with the optical film. The measurement was performed by measuring the Y value of the screen. The results are shown in Table 1.

A: The luminance improvement rate is 25% or more when the optical film is not attached.

B: The luminance improvement rate is 20% or more but less than 25% when the optical film is not attached

C: The luminance improvement rate is 15% or more and less than 20% with respect to the case where no optical film is attached.

D: The luminance improvement rate is less than 15% with respect to the case where no optical film is attached.

TABLE 1

Claims (11)

A manufacturing method of an organic EL image display device comprising a light emitting element substrate having an organic electroluminescent layer arranged in a matrix and an optical functional resin layer including a portion corresponding to the organic electroluminescent layer in a matrix form.
Providing an adhesive layer on any one surface of a film containing said optical functional resin layer or one surface of said light emitting element substrate,
Placing the film on the light emitting element substrate so that the adhesive layer is disposed between the film and the light emitting element substrate, and performing alignment of the organic electroluminescent layer and the corresponding portion while applying tension to the film; and
Bonding the film to the light emitting device substrate by curing the adhesive layer using heating or ultraviolet irradiation in the aligned state;
The adhesive layer is provided by transfer from a transfer film comprising the adhesive layer,
The film containing the optical functional resin layer is prepared to include the corresponding portion at a pitch smaller than the pitch of the organic electroluminescent layer in the direction parallel to the direction of the tension load in the tension unloaded state. The manufacturing method of an image display apparatus. The method according to claim 1,
The film containing the said optical functional resin layer is roll shape, and the direction of the said tension load is the long axis direction of the film containing the said optical functional resin layer, The manufacturing method of the organic electroluminescent image display apparatus. The method according to claim 1 or 2,
The manufacturing method of the organic electroluminescent image display apparatus of which the said light emitting element substrate is in roll shape, and the direction of the said tension load is the long axis direction of the said light emitting element substrate. The method according to claim 1 or 2,
The manufacturing method of the organic electroluminescent image display apparatus including the process of providing the said contact bonding layer in the surface of any one of the said light emitting element substrates. The method according to claim 1 or 2,
The manufacturing method of the organic electroluminescent image display apparatus whose thickness of the said contact bonding layer is 2.0 micrometers-30 micrometers. The method according to claim 1 or 2,
The said adhesive layer contains the weight average molecular weight 50,000-500,000 thermoplastic resin, the polymeric compound containing an ethylenically unsaturated double bond, and the polymerization initiator, The manufacturing method of the organic electroluminescent image display apparatus. The method according to claim 6,
The method for manufacturing an organic EL image display device, wherein the adhesive layer further contains a fluorine-based surfactant. The method according to claim 1 or 2,
The said hardening is hardening by an ultraviolet-ray, The manufacturing method of the organic electroluminescent image display apparatus. The method according to claim 1 or 2,
The optical functional resin layer is a polarization separation layer,
The manufacturing method of the organic electroluminescent image display apparatus whose said site | part is a polarization separation site which reflects the light of one polarization state, and transmits the light of the other polarization state among the light which the corresponding said organic electroluminescent layer emitted. . The method according to claim 9,
A method for producing an organic EL image display device, wherein the polarization separation portion is formed of a layer formed by fixing a cholesteric liquid crystal phase. The method according to claim 9,
The film further comprises a retardation layer and a polarizing layer,
The polarizing separation layer, the retardation layer, and the polarizing layer are arranged in this order from the facing side.

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