KR102481311B1 - Composition, retardation film for organic electroluminescence display device, method for manufacturing retardation film for organic electroluminescence display device - Google Patents

Abstract

The present invention is a composition capable of forming a retardation film at a predetermined position on an organic EL display element and having excellent display performance of an organic EL display device to which the retardation film is applied, a retardation film for an organic EL display element, and a retardation film for an organic EL display element. A method for producing a membrane is provided. The composition of the present invention is a composition for forming a retardation film disposed on an organic electroluminescent display device, which includes a polymer having a hydrophilic group, a crosslinkable group, and a mesogenic group, and a polymerizable compound.

Description

Composition, retardation film for organic electroluminescence display device, method for manufacturing retardation film for organic electroluminescence display device

The present invention relates to a composition, a retardation film for an organic electroluminescence display device, and a method for manufacturing the retardation film for an organic electroluminescence display device.

A retardation film having refractive index anisotropy is applied to various applications such as an antireflection film of a display device and an optical compensation film of a liquid crystal display device. In particular, recently, in order to suppress adverse effects caused by reflection of external light, a circular polarizing plate including a retardation film is used in an organic electroluminescence (EL) display device (Patent Document 1).

Japanese Unexamined Patent Publication No. 9-127885

Conventionally, when manufacturing an organic EL display device including a retardation film, as shown in FIG. 1 , an organic EL display element 16 including an organic light emitting layer 12 and connection terminals 14 on a mother substrate 10 make multiple copies of Regarding the configuration of the organic EL display element 16, in order to simplify the description, members other than the organic light emitting layer and the connecting terminal (for example, a pair of electrodes sandwiching the organic light emitting layer, a sealing layer, etc.) omit

Next, the mother substrate is cut to produce laminated bodies including the substrate 20 and the organic EL display element 16 as shown in FIG. 2 . Further, as shown in FIG. 3 , a phase contrast film 24 is bonded to the upper side of the organic light emitting layer 12 of the organic EL display element 16 via the adhesive layer 22 . Normally, when attaching the phase difference film 24, the phase difference film 24 is disposed so as not to cover the connection terminal 14 for connecting to the IC (Integrated Circuit) of the organic EL display element 16.

On the other hand, in recent years, the aspect of directly forming a retardation film on an organic EL display element is desired from the point of thinning an organic EL display device and improving flexibility. At this time, a method of forming a retardation film by applying a composition for forming a retardation film onto an organic EL display element can be considered.

However, when a conventional composition for forming a retardation film is used, the retardation film is formed to cover the connection terminals of the above-described organic EL display device, and thus the retardation film cannot be formed only at a desired position.

In view of the above circumstances, an object of the present invention is to provide a composition capable of forming a retardation film at a predetermined position on an organic EL display element and having excellent display performance of an organic EL display device to which the retardation film is applied.

Moreover, this invention also makes it a subject to provide the manufacturing method of the retardation film for organic EL display elements, and the retardation film for organic EL display elements.

As a result of earnestly examining the problems of the prior art, the present inventors have found that the above problems can be solved by using a composition having a predetermined composition.

That is, it discovered that the said subject was solvable by the following structure.

(1) a polymer having a hydrophilic group, a crosslinkable group, and a mesogenic group;

containing polymeric compounds,

A composition for forming a retardation film disposed on an organic electroluminescence display device.

(2) The composition according to (1), wherein the polymer contains a repeating unit having a crosslinkable group and a mesogenic group.

(3) The composition according to (1) or (2), wherein the hydrophilic group and the crosslinkable group can react by heating.

(4) The composition according to any one of (1) to (3), wherein the crosslinkable group is a group selected from the group consisting of an oxetanyl group and an epoxy group.

(5) The composition according to any one of (1) to (4), wherein the hydrophilic group is a group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group.

(6) The composition according to any one of (1) to (5), further comprising a polymerization initiator.

(7) The composition according to any one of (1) to (6), wherein the polymerizable compound is a polymerizable liquid crystal compound.

(8) A retardation film for an organic electroluminescence display element formed using the composition according to any one of (1) to (7).

(9) The retardation film for an organic electroluminescence display element according to (8), which is a λ/4 plate or a λ/2 plate.

(10) The retardation film for organic electroluminescence display elements according to (8) or (9), which exhibits reverse wavelength dispersion.

(11) an organic electroluminescence display element;

An organic electroluminescence display device comprising the retardation film for an organic electroluminescence display element according to any one of (8) to (10), disposed on an organic electroluminescence display element.

(12) a step of forming a coating film on a substrate on which an organic electroluminescence display element is disposed, using the composition according to any one of (1) to (7);

A step of orienting the mesogen groups in the coating film;

A step of exposing a part of the coating film;

A method for producing a retardation film for an organic electroluminescence display element, comprising a step of developing the exposed coating film and forming a retardation film for the organic electroluminescence display element on the organic electroluminescence display element.

According to the present invention, it is possible to provide a composition capable of forming a retardation film at a predetermined position on an organic EL display element and having excellent display performance of an organic EL display device to which the retardation film is applied.

Moreover, according to this invention, the manufacturing method of the retardation film for organic EL display elements and the retardation film for organic EL display elements can be provided.

1 is a diagram showing a manufacturing process of a prior art organic EL display device.
Fig. 2 is a diagram showing a manufacturing process of a prior art organic EL display device.
Fig. 3 is a diagram showing a manufacturing process of a prior art organic EL display device.
4 is a diagram for explaining the procedure of step 1;
5 is a diagram for explaining the procedure of step 3;
6 is a diagram for explaining the procedure of step 4;

Hereinafter, the present invention will be described in detail. In addition, the numerical range expressed using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. First, terms used in this specification will be described.

In the present invention, Re(λ) and Rth(λ) represent in-plane retardation and thickness direction retardation at wavelength λ, respectively. When there is no description in particular, the wavelength λ is 550 nm.

In the present invention, Re(λ) and Rth(λ) are values measured at a wavelength λ in AxoScanOPMF-1 (manufactured by Opto Science). By inputting the average refractive index ((nx + ny + nz) / 3) and the film thickness (d (μm)) with AxoScan,

Slow axis direction (°)

Re(λ)=R0(λ)

Rth(λ)=((nx+ny)/2-nz)×d

is calculated

In addition, R0(λ) is expressed as a numerical value calculated by AxoScanOPMF-1, but means Re(λ).

In this specification, the refractive indices nx, ny, and nz are measured using an Abbe refractive index (NAR-4T, manufactured by Atago Co., Ltd.) and using a sodium lamp (λ = 589 nm) as a light source. In the case of measuring the wavelength dependence, it can be measured with a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) in combination with an interference filter.

In addition, values from the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. The values of the average refractive index of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).

In addition, in this specification, Nz factor is a value given by Nz=(nx-nz)/(nx-ny).

In addition, in this specification, "visible light" refers to light with a wavelength of 380 to 780 nm.

In addition, in this specification, regarding angles (eg, angles such as "90°") and their relationships (eg, "orthogonal", "parallel", and "intersect at 45°", etc.), the present invention It is assumed that the range of error allowed in the technical field to which this belongs is included. For example, it means within the range of the exact angle ±10°, etc., and the error from the exact angle is preferably 5° or less, more preferably 3° or less.

In this specification, the "absorption axis" of a polarizer means the direction in which absorbance is the highest. The "transmission axis" means a direction forming an angle of 90° with the "absorption axis".

Characteristics of the composition for forming a retardation film disposed on the organic electroluminescence display device of the present invention (composition for forming a retardation film for organic electroluminescence) (hereinafter, simply referred to as "the composition of the present invention") One example is the use of a polymer having a hydrophilic group, a crosslinkable group, and a mesogenic group.

When the polymer has a hydrophilic group, developability is imparted to a coating film described in detail in a later paragraph. Further, when the polymer has a crosslinkable group, phase separation between the polymers and/or between the polymer and the polymerizable compound can be suppressed, resulting in excellent display performance of the organic EL display device. Moreover, phase difference can be expressed because a polymer has a mesogen group. Further, when the composition of the present invention contains a polymerizable liquid crystal compound, the polymer having a mesogen group provides excellent compatibility between the polymer and the polymerizable liquid crystal compound, and the removal of the coating film by the developing solution proceeds efficiently.

The composition of the present invention includes a polymer having a hydrophilic group, a crosslinkable group, and a mesogenic group, and a polymerizable compound.

Hereinafter, each component included in the composition of the present invention will be described in detail.

<Polymer having a hydrophilic group, a crosslinkable group, and a mesogenic group>

A polymer has a hydrophilic group.

As a hydrophilic group, a carboxy group, a hydroxyl group, a sulfo group, and an amino group are mentioned, for example. Especially, a carboxy group or a phenolic hydroxyl group is preferable, and a carboxy group is more preferable at the point which has more excellent reactivity with the crosslinkable group mentioned later.

In addition, with a phenolic hydroxyl group, a hydroxyl group directly bonded to an aromatic hydrocarbon ring group is intended.

The polymer preferably contains a repeating unit having a hydrophilic group. The number of hydrophilic groups in each repeating unit is not particularly limited, and may be one or plural (two or more).

Moreover, only 1 type of hydrophilic group may be sufficient as it, and 2 or more types may be sufficient as it.

As the repeating unit having a hydrophilic group, a repeating unit represented by Formula (1) is preferable.

[Formula 1]

R ¹ represents a hydrogen atom or an alkyl group.

L ¹ represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include any one group selected from the group consisting of -O-, -CO-, -NR ^A -, and divalent hydrocarbon groups, or groups combining two or more groups. can R ^A represents a hydrogen atom or an alkyl group.

Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group (eg -CH=CH-), an alkynylene group (eg -C≡C-), and an arylene group (eg phenylene group). ) can be heard. As said alkylene group, any of linear, branched chain, and cyclic|annular may be sufficient. Moreover, as for the carbon number, 1-10 are preferable, 1-6 are more preferable, and 1-4 are still more preferable.

X represents a hydrophilic group. The definition of the hydrophilic group is as described above.

Further, as described above, the polymer preferably contains a repeating unit having a carboxy group or a phenolic hydroxyl group.

As a repeating unit which has a carboxy group, the repeating unit derived from an unsaturated carboxylic acid is mentioned. Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids and unsaturated polyvalent carboxylic acids.

As an unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl-succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and 2-(meth)acryloyloxyethyl-phthalic acid.

Moreover, as an unsaturated polyhydric carboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid are mentioned, for example.

Moreover, the acid anhydride may be sufficient as the unsaturated polyhydric carboxylic acid. Specifically, maleic acid anhydride, itaconic acid anhydride, and citraconic acid anhydride are mentioned.

Further, the unsaturated polyvalent carboxylic acid may be a mono(2-methacryloyloxyalkyl) ester of a polyhydric carboxylic acid, for example, mono(2-acryloyloxyethyl) succinate, mono(2-methacrylic acid) succinate royloxyethyl), phthalic acid mono(2-acryloyloxyethyl), and phthalic acid mono(2-methacryloyloxyethyl).

Further, the unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of dicarboxypolymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. can

Moreover, as an unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic-acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, and 4-carboxy styrene are also mentioned.

Specific examples of the repeating unit having a carboxy group include the following.

[Formula 2]

As a repeating unit which has a phenolic hydroxyl group, the repeating unit represented by Formula(1-1) is mentioned.

[Formula 3]

R ¹¹ represents a hydrogen atom or an alkyl group.

L ¹¹ represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L ¹ described above.

R ¹² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a+b is 5 or less.

Further, when two or more R ¹² are present, these R ¹² may be different from each other or may be the same.

The content of the repeating unit having a hydrophilic group in the polymer is not particularly limited, but at least one of easier formation of a retardation film at a predetermined position and better display performance of an organic EL display device to which the retardation film is applied is obtained. In terms of the point (hereinafter also referred to simply as "the point where the effect of the present invention is more excellent"), 5 to 40% by mass is preferable, and 10 to 30% by mass relative to the mass (100% by mass) of all repeating units in the polymer. is more preferable.

As for the repeating unit having a hydrophilic group, only 1 type may be used, and 2 or more types may be used.

The polymer has a crosslinkable group. In addition, a crosslinkable group is a group different from a hydrophilic group.

Examples of the crosslinkable group include oxetanyl group, epoxy group, acryloyl group, methacryloyl group, thiol group, halogenated benzyl group, carboxylic acid anhydride group, cyanate ester group, isocyanate group, and aldehyde group. , an aziridine group, and an alkoxysilyl group.

In addition, as a combination of a hydrophilic group and a crosslinkable group, it is preferable that the hydrophilic group and the crosslinkable group can react by heating from the viewpoint of better chemical resistance of the retardation film. Examples of such a combination of a hydrophilic group and a crosslinkable group include a combination of a carboxy group and an oxetanyl group, a combination of a carboxy group and an epoxy group, a combination of a phenolic hydroxyl group and an oxetanyl group, and a combination of a phenolic hydroxyl group and an epoxy group. .

It is preferable that the polymer contains a repeating unit having a crosslinkable group.

As a repeating unit which has a crosslinkable group, the repeating unit represented by Formula (2) is preferable.

[Formula 4]

R ² represents a hydrogen atom or an alkyl group.

L ² represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L ¹ described above.

In addition, as described in detail in the following paragraphs, the repeating unit having a crosslinkable group may have both a mesogen group, and for example, L ² may contain a mesogen group.

Y represents a crosslinkable group. The definition of the crosslinkable group is as described above.

The content of the repeating unit having a crosslinkable group in the polymer is not particularly limited, but is preferably 5 to 85% by mass, and 20 to 80% by mass relative to the mass of all repeating units in the polymer, from the viewpoint of more excellent effects of the present invention. Mass % is more preferred.

As for the repeating unit which has a crosslinkable group, only 1 type may be used and 2 or more types may be used.

A polymer has a mesogen group.

A mesogenic group is a functional group that is rigid and has orientation. As the structure of the mesogenic group, for example, a group selected from the group consisting of an aromatic ring group (aromatic hydrocarbon ring group and an aromatic heterocyclic group) and an alicyclic group, a plurality of, direct or divalent linking groups (eg -CO-, -O -, -NR ^A - (R ^A represents a hydrogen atom or an alkyl group), or a group combining these).

More specifically, as a mesogen group, the group represented by Formula (A) is mentioned.

Formula (A) -(L ^a -L ^b ) _n -

L ^a represents a divalent aromatic ring group or a divalent alicyclic group.

As a divalent aromatic ring group, a divalent aromatic hydrocarbon ring group (eg, phenylene group) or a divalent aromatic heterocyclic group is mentioned.

As a divalent alicyclic group, a cyclohexylene group is mentioned.

L ^b represents a single bond, -CO-, -O-, -NR ^A - or a group combining these (for example, -CO-O-). R ^A represents a hydrogen atom or an alkyl group.

n represents an integer of 2 or greater. Especially, 2-5 are preferable and 2-3 are more preferable.

It is preferable that the polymer contains a repeating unit having a mesogen group.

The content of the repeating unit having a mesogenic group in the polymer is not particularly limited, but is preferably 5 to 85% by mass, and preferably 20 to 80%, based on the mass of all repeating units in the polymer, from the viewpoint of more excellent effects of the present invention. Mass % is more preferred.

As for the repeating unit which has a mesogen group, only 1 type may be used, and 2 or more types may be used.

In the polymer, two or more selected from the group consisting of a hydrophilic group, a crosslinkable group, and a mesogenic group may be included in the same repeating unit. Especially, it is preferable that the polymer contains the repeating unit which has a crosslinkable group and a mesogenic group from the point which the effect of this invention is more excellent. As a repeating unit which has a crosslinkable group and a mesogen group, the repeating unit represented by Formula (3) is mentioned.

[Formula 5]

The definitions of L ^a , L ^b , and n are as described in Formula (A).

R ³ represents a hydrogen atom or an alkyl group.

L ³ and L ⁴ represent a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L ¹ described above.

In addition, as a divalent linking group represented by L ³ and L ⁴ , for example, -CO-O-, -CO-O-alkylene group, -CO-O-alkylene group-O-, -O-alkylene group-O -, -(O-alkylene group) _m -, and -CO-O-(alkylene group-O) _m -. m represents an integer of 2 or more, and the upper limit is not particularly limited, but 5 or less is preferable.

Z represents a crosslinkable group. The definition of the crosslinkable group is as described above.

The content of the repeating unit having a crosslinkable group and a mesogenic group in the polymer is not particularly limited, but is preferably 50 to 95% by mass with respect to the mass of all repeating units in the polymer from the viewpoint of more excellent effects of the present invention, 60-90 mass % is more preferable.

As for the repeating unit which has a crosslinkable group and a mesogen group, only 1 type may be used, and 2 or more types may be used.

The following are mentioned as a monomer which comprises the repeating unit represented by Formula (3) by superposition|polymerization. Moreover, one acryloyl group in the following monomers polymerizes, and the repeating unit represented by Formula (3) is comprised.

[Formula 6]

The polymer may contain repeating units other than the repeating units described above (repeating units having a hydrophilic group, repeating units having a crosslinkable group, repeating units having a mesogenic group, and repeating units having a crosslinkable group and a mesogenic group).

Examples of monomers capable of constituting other repeating units include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, aryl (meth)acrylates, diesters of unsaturated dicarboxylic acids, and bicyclounsaturated compounds. , maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, and other unsaturated compounds.

1000-200000 are preferable and, as for the weight average molecular weight of a polymer, 2000-50000 are more preferable in polystyrene conversion weight average molecular weight.

Moreover, 1.0-5.0 are preferable and, as for ratio (dispersion degree) of a number average molecular weight and a weight average molecular weight, 1.0-3.5 are more preferable.

In the measurement by the GPC (Gel Permeation Chromatography) method, for example, using HLC-8120 (manufactured by Tosoh Corporation), TSKgel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column was used as an eluate. As such, THF (tetrahydrofuran) can be used.

The acid value of the polymer is not particularly limited, but is preferably 20 to 300 mgKOH/mg, and more preferably 50 to 250 mgKOH/mg, from the viewpoint of more excellent effects of the present invention.

The method for synthesizing the polymer is not particularly limited, and known methods may be used. For example, there is a method of polymerizing a mixture including a radical polymerizable monomer having a hydrophilic group, a radical polymerizable monomer having a crosslinkable group, and a radical polymerizable monomer having a mesogen group in an organic solvent using a radical polymerization initiator. .

The content of the polymer in the composition of the present invention is not particularly limited, but is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content in the composition, from the viewpoint of more excellent effects of the present invention. And, 20 to 80% by mass is more preferable.

With solid content, a component capable of forming a phase contrast film is intended, and a solvent is not contained. In addition, even if the component capable of forming the retardation film is in a liquid state, it is treated as a solid component.

<Polymerizable compound>

A polymerizable compound is a compound having a polymerizable group.

The type of the polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.

As the radical polymerizable group, a known radical polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable.

As the cationic polymerizable group, a known cationic polymerizable group can be used, and specific examples include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. .

The number of polymerizable groups in the polymerizable compound is not particularly limited, but is preferably 6 or less.

Moreover, it is also preferable that a polymeric compound has both a radical polymerizable group and a cationic polymerizable group.

As a polymerizable compound, a multifunctional radically polymerizable compound is mentioned, for example. Specifically, the thing of Unexamined-Japanese-Patent No. 2002-296423, Paragraph [0018] - [0020] is mentioned.

As the polymerizable compound, a polymerizable liquid crystal compound is preferable. A polymerizable liquid crystal compound is a compound that has a polymerizable group and exhibits liquid crystallinity.

The type of polymerizable liquid crystal compound is not particularly limited, but it can be classified into rod-shaped liquid crystal compounds (rod-like liquid crystal compounds) and disk-shaped liquid crystal compounds (discotic liquid crystal compounds) based on their shape. In addition, there are a low molecular type and a high molecular type, respectively. Polymers generally refer to those having a polymerization degree of 100 or higher (Polymer Physics/Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In addition, two or more types of rod-like liquid crystal compounds, two or more types of discotic liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a discotic liquid crystal compound may be used.

The content of the polymerizable compound in the composition of the present invention is not particularly limited, but is preferably 5 to 85% by mass, and 20 to 70% by mass relative to the total solid content in the composition, from the viewpoint of more excellent effects of the present invention. more preferable

<Others>

The composition of the present invention may contain other components other than the above-mentioned polymer and polymerizable compound.

For example, the composition of the present invention may contain a polymerization initiator. The polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include thermal polymerization initiators and photopolymerization initiators. For example, as a photoinitiator, an α-carbonyl compound, an acyloin ether, an α-hydrocarbon substituted aromatic acyloin compound, a polynuclear quinone compound, and a triaryl imidazole dimer and p-amino Combinations of phenyl ketones are exemplified.

0.01-20 mass % is preferable with respect to the total solids of a composition, and, as for content of the polymerization initiator in the composition of this invention, 0.5-5 mass % is more preferable.

Moreover, the composition of this invention may contain surfactant.

Examples of the surfactant include conventionally known compounds, but fluorine-based compounds are preferable. For example, the compound described in paragraph [0028] - [0056] in Unexamined-Japanese-Patent No. 2001-330725, and the compound described in paragraph [0069] - [0126] in Japanese Patent Application No. 2003-295212 are mentioned.

In addition, the composition of the present invention may contain a curing agent having a reactive group capable of reacting with a crosslinkable group. The number of reactive groups in the curing agent is not particularly limited, but is preferably two or more, and more preferably 2 to 6.

The kind of reactive group is not particularly limited, and an optimal group is selected depending on the kind of crosslinkable group. For example, when a crosslinkable group is an oxetanyl group, a carboxy group is mentioned as a reactive group.

Moreover, the composition of this invention may contain the solvent. As a solvent, an organic solvent is preferable. Examples of organic solvents include amides (eg N,N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl Halides (e.g. chloroform, dichloromethane), esters (e.g. methyl acetate, ethyl acetate, butyl acetate), ketones (e.g. acetone, methylethylketone), and ethers (e.g. tetrahydrofuran, 1,2 -dimethoxyethane). Moreover, you may use together two or more types of organic solvents.

Moreover, the composition may contain various orientation control agents, such as a vertical alignment agent and a horizontal alignment agent. These alignment control agents are compounds capable of controlling the alignment of the polymerizable liquid crystal compound horizontally or vertically on the interface side. In addition, a chiral agent may be included in the composition, and in this case, a twist nematic phase or a cholesteric phase can be developed.

Moreover, the composition may contain an adhesion improving agent, a pigment, a plasticizer, etc. other than the said component.

<Method for manufacturing phase contrast film>

The composition of the present invention is used to form a phase contrast film disposed on an organic EL display element. As described above, by using the composition of the present invention, a phase contrast film can be formed at a predetermined position.

The method for forming the retardation film for organic EL display elements of the present invention has the following steps 1 to 4.

Step 1: Step of bringing the composition of the present invention into contact with a substrate on which an organic EL display element is disposed to form a coating film

Step 2: Step of orienting the mesogen groups in the coating film

Process 3: Process of exposing a part of the coating film

Step 4: Step of developing the exposed coating film and forming a retardation film on the organic EL display element

Hereinafter, the order of each process is demonstrated in detail.

(Process 1)

Step 1 is a step of forming a coating film on a substrate on which an organic EL display element is disposed, using the composition of the present invention. By carrying out this process, as shown in FIG. 4, the laminated body which consists of the board|substrate 30, the organic EL display element 32 containing an organic light emitting layer, and the coating film 34 is obtained.

The type of substrate supporting the organic EL display element is not particularly limited, and examples thereof include a glass substrate, a metal substrate, a ceramic substrate, a semiconductor substrate, and a resin substrate.

The structure of the organic EL display element is not particularly limited, but usually includes at least a pair of electrodes (cathode and anode) and an organic light emitting layer disposed between the electrodes.

In addition, an organic EL display element usually includes a connection terminal for connecting to an IC together with an organic light emitting layer. In addition, the organic EL display element may include other members, and may include, for example, a sealing layer covering the organic light emitting layer.

Moreover, several organic EL display elements may be arrange|positioned like FIG. 1 on a board|substrate.

The method of forming a coating film using the composition of the present invention is not particularly limited, and examples thereof include a method of applying the composition of the present invention onto the substrate. Examples of the coating method include a curtain coating method, a spin coating method, a slit coating method, a print coating method, a spray coating method, a blade coating method, a gravure coating method, and a wire bar method.

In addition, you may form an orientation layer on the board|substrate on which the organic electroluminescent display element was arrange|positioned before forming a coating film using the composition of this invention as needed. The orientation layer should just be arranged at least above the organic light emitting layer in the organic EL display element (on the side opposite to the substrate), and is preferably not arranged on the connection terminal.

An alignment layer generally has a polymer as a main component. As the polymer for the orientation layer, it is described in many literatures, and many commercial items are available. The polymer used is preferably polyvinyl alcohol (PVA), polyimide or a derivative thereof.

Moreover, as an orientation layer, the layer to which the well-known rubbing process was given is preferable. Moreover, you may use a photo-alignment layer as an orientation layer.

In particular, when forming regions with different alignment directions within the surface of the retardation film, it is preferable to use a photo-alignment layer because patterning can be easily realized by adjusting the polarization axis of polarized light irradiation in the photo-alignment treatment.

A known material can be used as the photo-alignment layer, but if a photocurable photo-alignment layer is used, heat is not applied to the substrate, and surface failures caused by rubbing scraps and film pieces generated during peeling are not accompanied, resulting in high quality It is preferable because it can form an alignment layer of

As such a material, a composition for forming an optical alignment layer containing, for example, a polymer having an optical alignment group, a polymerizable monomer, and a photopolymerization initiator can be used. Specifically, the composition described in Paragraph 0241 of Unexamined-Japanese-Patent No. 2014-533376, Paragraph 0087 of Unexamined-Japanese-Patent No. 2015-527615, and Paragraph 0134 of Unexamined-Japanese-Patent No. 2016-535158 is mentioned.

The thickness of the alignment layer is preferably 0.01 to 10 μm.

In addition, the orientation layer may be removed together at step 4 described later.

In addition, in the case of the photocurable alignment film described above, after preventing photocuring by shielding light or the like for regions where the coating film is to be removed in step 4 described later, such as wiring connections, the substrate is coated with an appropriate solvent prior to step 2 described later. Alternatively, the alignment film may be removed in advance by rinsing with a developing solution or the like. By doing this, when the retardation film is removed in step 4, a state in which the corresponding region on the substrate is exposed is realized.

(Process 2)

Step 2 is a step of orienting the mesogen groups in the coating film. In addition, in the case where the polymerizable liquid crystal compound is contained in the coating film, both the mesogenic group and the polymerizable liquid crystal compound are oriented in Step 2.

As the specific processing method (orientation treatment) of step 2, a method of heating the coating film and a method of drying the coating film at room temperature are exemplified. In the case of a thermotropic liquid crystal compound, the liquid crystal phase formed by alignment treatment can generally be transformed by a change in temperature. In the case of a lyotropic liquid crystal compound, it can be made to transition also according to the composition ratio, such as the amount of solvent.

In addition, although the conditions in the case of heating a coating film are not specifically limited, 50-150 degreeC is preferable as a heating temperature, and 10 seconds - 5 minutes are preferable as a heating time.

(Process 3)

Step 3 is a step of exposing a part of the coating film. In this process, as shown in FIG. 5 , a part of the area of the coating film 34 is exposed. In the exposed portion 36, polymerization of the polymerizable compound proceeds, and it becomes insoluble with respect to the developing solution used in step 4 described later. On the other hand, in the unexposed portion 38, the polymerization of the polymerizable compound does not proceed, and the developing solution used in Step 4 remains available.

In addition, in order to form a retardation film on the upper side of the organic light emitting layer in the organic EL display element, it is preferable to expose a region of the coating film located on the upper side of the organic light emitting layer. In Fig. 5, the exposed portion of the coating film coincides with the area of the coating film located above the organic light emitting layer. In addition, in order not to form a retardation film on the connection terminal included in the organic EL display element, it is preferable not to expose the coating film on the connection terminal. That is, in this step, at least the area of the coating film located above the organic light emitting layer in the organic EL display element is exposed, and the area of the coating film located above the connection terminal in the organic EL display element is preferably not exposed.

The type of light used for exposure is not particularly limited, but ultraviolet light is preferred.

The method of exposure is not particularly limited, and examples thereof include a method of exposing a coating film through a mask having a predetermined opening.

The amount of irradiation during exposure is not particularly limited, and is preferably 10 mJ/cm ² to 50 J/cm ² and more preferably 20 mJ/cm ² to 5 J/cm ² . Moreover, in order to promote a polymerization reaction, you may carry out under heating conditions.

In addition, depending on the kind of crosslinkable group, the crosslinkable group may react by performing step 3. For example, when the crosslinkable group is an acryloyl group or a methacryloyl group and the radical polymerization reaction proceeds by exposure, the reaction of the crosslinkable group also proceeds.

(Process 4)

Step 4 is a step of developing the exposed coating film and forming a retardation film on the organic EL display element. By carrying out this process, as shown in FIG. 6, only the exposed area remains, and in particular, a phase contrast film 40 (for organic EL display element) is formed above the organic light emitting layer (not shown) in the organic EL display element 32. phase contrast film) is preferably formed.

In addition, as described above, by unexposing the region of the coating film located on the connection terminal in the organic EL display element, the coating film in that region can be removed in this step, so that the phase difference film is not formed on the connection terminal. can

The type of developer used for development is not particularly reduced, and an optimum developer (e.g., an alkaline developer and a developer containing an organic solvent) is selected depending on the type of coating film. Among them, an alkaline developer is preferable from the viewpoint of better removability of the coating film.

As an alkaline developing solution, the aqueous solution containing an alkali is mentioned. Examples of the alkali developing solution include quaternary ammonium salts typified by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, and alkaline aqueous solutions containing cyclic amines. there is. Among them, as an alkaline developing solution, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is preferable. You may add an appropriate amount of alcohols and/or surfactant to alkaline developing solution. As for the alkali concentration of an alkali developing solution, 0.1-20 mass % is preferable. Moreover, as for pH of alkaline developing solution, 10.0-15.0 are preferable.

The method of the developing treatment is not particularly limited, as long as the exposed coating film and the developing solution can come into contact. Examples include a method of applying a developing solution on the coating film and a method of immersing a laminate having a coating film in the developing solution. there is.

Moreover, you may perform a rinse process using a rinse liquid after image development as needed. As a rinse liquid, pure water is mentioned.

Further, if necessary, heat treatment may be performed on the developed coating film. By carrying out heat treatment (post-bake treatment), the crosslinkable group can be reacted and the chemical resistance of the retardation film can be improved. In addition, as described above, when the crosslinkable group and the hydrophilic group can react by heating, both react by performing the main treatment.

The temperature of the heat treatment is not particularly limited, and is preferably 70 to 250°C, more preferably 80 to 200°C. The heat treatment time is not particularly limited, and is preferably 5 to 180 minutes, more preferably 10 to 120 minutes.

According to the above method, a retardation film for an organic EL display element can be formed at a predetermined position of the organic EL display element.

The in-plane retardation of the retardation film for organic EL display elements formed using the composition of the present invention is not particularly limited, and an optimum value is selected depending on the intended use. Among them, it is preferable that the retardation film is a λ/4 plate or a λ/2 plate in view of being used as a retardation film of a circular polarizing plate described later.

A λ/4 plate (a plate having a λ/4 function) is a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). More specifically, it is a plate whose in-plane retardation at a predetermined wavelength λ nm is λ/4 (or an odd multiple of this).

Especially, the in-plane retardation Re(550) at a wavelength of 550 nm is preferably 100 to 200 nm, and more preferably 120 to 160 nm, from the viewpoint of more excellent function as a circular polarizing plate.

Further, the λ/2 plate refers to an optically anisotropic layer in which the in-plane retardation Re(λ) at a specific wavelength λ nm satisfies Re(λ) ≈ λ/2. Especially, as for in-plane retardation Re(550) in wavelength 550nm, 210-300nm is preferable.

It is preferable that the retardation film for organic EL display elements formed using the composition of the present invention exhibits reverse wavelength dispersion (a characteristic in which in-plane retardation increases as the measurement wavelength increases).

In addition, a plurality of retardation films for organic EL display elements may be laminated by performing the above method a plurality of times. That is, using the composition of the present invention, only one layer or two or more phase contrast films may be formed at a predetermined position of the organic EL display element. When two or more layers are formed, for example, a lamination of a λ/2 plate exhibiting forward wavelength dispersion in wavelength dispersion characteristics and a λ/4 board exhibiting forward wavelength dispersion in wavelength dispersion characteristics, and reverse wavelength dispersion and lamination of a λ/4 plate and a positive C plate.

In addition, a phase contrast film having other functions can be formed by adding an additive such as a pigment to the composition of the present invention within a range not departing from the spirit of the present invention.

For example, a phase contrast film exhibiting a twisted nematic phase or a cholesteric phase may be provided as the phase contrast film. Such a retardation film imparts, for example, a function of rotating a polarization axis as a polarization layer, or imparts an effect intended to improve brightness or color reproducibility as a wavelength selective reflection film. Such a retardation film can be obtained by adding a known chiral agent to the composition of the present invention. Further, a retardation film exhibiting a cholesteric phase can also be used as a C plate (nx≒ny<nz, or nx≒ny>nz) for light of a specific wavelength.

In addition, when the retardation film contains various dyes, color reproducibility can be improved or display performance can be improved by providing visual effects. Such a dye-containing phase contrast film can be obtained by adding a dye to the composition of the present invention. For example, a dye having an absorption peak at a wavelength of 480 to 520 nm or a wavelength of 580 to 620 nm is useful for expanding the color reproduction range.

In addition, by orienting the dichroic dye using the orientation of the liquid crystal compound of the composition of the present invention using the dichroic dye as the dye, in particular, anisotropy (in-plane direction or oblique direction) of the light absorption property is imparted to improve display performance. can improve

<Organic EL display device>

By the method described above, an organic EL display device including an organic EL display element and a retardation film for the organic EL display element disposed on the organic EL display element is fabricated. Further, it is preferable that the retardation film for the organic EL display element is disposed so as to directly contact the organic EL display element.

It is preferable that the organic EL display device further include a polarizer on the retardation film for organic EL display elements. For example, when the retardation film for organic EL display elements functions as a λ/4 plate, the polarizer and the retardation film for organic EL display elements are combined to function as a circular polarizing plate. Further, when laminating a λ/4 plate retardation film for an organic EL display element and a polarizer, it is preferable to adjust the angle formed by the in-plane slow axis of the retardation film for an organic EL display element and the absorption axis of the polarizer to be 45±10°. .

By disposing the circularly polarizing plate on the organic EL display element, reflection of external light is prevented.

The polarizer may be a member (linear polarizer) having a function of converting light into a specific linearly polarized light, and an absorption type polarizer is exemplified.

As an absorption type polarizer, an iodine type polarizer, a dye type polarizer using a dichroic dye, and a polyene type polarizer are mentioned, for example. An iodine-based polarizer and a dye-based polarizer include a coating type polarizer and a stretching type polarizer, and both can be applied. Especially, a polarizer produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching is preferable.

In addition, as a method of obtaining a polarizer by stretching and dyeing in a laminated film state in which a polyvinyl alcohol layer is formed on a substrate, Japanese Patent Publication No. 5048120, Japanese Patent Publication No. 5143918, Japanese Patent Publication No. 5048120, Japan The methods described in Japanese Patent Publication No. 4691205, Japanese Patent Publication No. 4751481, and Japanese Patent Publication No. 4751486 can be cited, and known techniques relating to these polarizers can also be preferably used.

Among them, from the viewpoint of handleability, the polarizer is a polyvinyl alcohol-based resin (a polymer containing -CH ₂ -CHOH- as a repeating unit, in particular, at least selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers It is preferable that it is a polarizer containing one).

The thickness of the polarizer is not particularly limited, but is preferably 35 µm or less, and more preferably 3 to 25 µm, in view of excellent handling properties and excellent optical properties.

Example

The present invention will be described in more detail by way of examples below. The materials, usage amount, ratio, processing details, and processing procedures 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 specific examples shown below.

<Synthesis Example 1: Polymer 1>

Methyl ethyl ketone was put into the flask, and the temperature was raised to 70°C in a nitrogen atmosphere. Into the flask, a solution obtained by mixing a predetermined amount of liquid crystal monomer 1, acrylic acid, ethyl acrylate, and V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. It stirred for 2 hours after completion|finish of dripping. Thus, Polymer 1 was obtained.

Regarding the content of each repeating unit in Polymer 1 with respect to all repeating units, the repeating unit derived from the liquid crystal monomer 1 was 70% by mass, the repeating unit derived from acrylic acid was 13% by mass, and the repeating unit derived from ethyl acrylate was 17% by mass. % was Moreover, the weight average molecular weight of polymer 1 was 15000. Moreover, the acid value of polymer 1 was 101 mgKOH/mg.

In addition, liquid crystal monomer 1 was synthesized with reference to Japanese Patent Publication No. 11-513019 (WO97/000600).

[Formula 7]

<Synthesis Example 2: Polymer 2>

Polymer 2 was synthesized according to the same procedure as in Synthesis Example 1, except that liquid crystal monomer 1 was changed to liquid crystal monomer 2.

In addition, the content, weight average molecular weight, and acid value of each repeating unit in Polymer 2 are the content and weight of each repeating unit in Polymer 1, respectively, except that the repeating unit derived from Liquid Crystal Monomer 1 is changed to the Repeating Unit derived from Liquid Crystal Monomer 2. It was the same as the average molecular weight and acid value.

In addition, liquid crystal monomer 2 was synthesized with reference to Japanese Patent Publication No. 11-513019 (WO97/000600).

[Formula 8]

<Synthesis Example 3: Polymer 3>

Polymer 3 was synthesized according to the same procedure as in Synthesis Example 1, except that liquid crystal monomer 1 was changed to liquid crystal monomer 3. Polymer 3 contained an acryloyl group as a crosslinkable group.

In addition, the content, weight average molecular weight, and acid value of each repeating unit in Polymer 3 are the content and weight of each repeating unit in Polymer 1, respectively, except for the fact that the repeating unit derived from Liquid Crystal Monomer 1 is changed to the Repeating Unit derived from Liquid Crystal Monomer 3. It was the same as the average molecular weight and acid value.

In addition, liquid crystal monomer 3 was synthesized with reference to Japanese Patent Publication No. 11-513019 (WO97/000600).

[Formula 9]

<Synthesis Example 4: Polymer C1>

Polymer C1 was synthesized according to the same procedure as in Synthesis Example 1, except that the liquid crystal monomer 1 was changed to the following monomer C1.

In addition, except for the fact that the repeating unit derived from the liquid crystal monomer 1 is changed to the repeating unit derived from the monomer C1, the content, weight average molecular weight, and acid value of each repeating unit in the polymer C1 are the content of each repeating unit in the polymer 1, the weight average It was the same as molecular weight and acid value.

[Formula 10]

<Synthesis Example 5: Polymer C2>

Polymer C2 was synthesized according to the same procedure as in Synthesis Example 1, except that acrylic acid was not used.

Regarding the content of each repeating unit in Polymer C2 with respect to all repeating units, the repeating unit derived from the liquid crystal monomer 1 was 70% by mass, and the repeating unit derived from ethyl acrylate was 30% by mass. Moreover, the weight average molecular weight of polymer C2 was 15000.

<Synthesis Example 6: Polymer C3>

Polymer C3 was synthesized according to the same procedure as in Synthesis Example 1, except that the liquid crystal monomer 1 was changed to glycidyl methacrylate.

In addition, the content of each repeating unit in Polymer C3, the weight average molecular weight, and the acid value, except for the fact that the repeating unit derived from the liquid crystal monomer 1 was changed to the repeating unit derived from glycidyl methacrylate, respectively, of each repeating unit in Polymer 1 It was the same as content, weight average molecular weight, and acid value.

<Example 1>

The following components were dissolved in methyl ethyl ketone, and the solid concentration was adjusted to 25% by mass to obtain a composition.

In addition, numerical values "83%", "15%" and "2%" in the structural formula of the liquid crystal monomer indicate the content (mass %) of each monomer relative to the total mass of the liquid crystal monomer.

Polymer 1 50 parts by mass

100 parts by mass of liquid crystal monomer

8 parts by mass of polyfunctional monomer

IRG907 (IRGACURE 907 (manufactured by BASF)) 6 parts by mass

F Polymer 1 0.25 parts by mass

F polymer 2 0.1 parts by mass

[Formula 11]

<Examples 2 to 4, Comparative Examples 1 to 3>

A composition was obtained according to the same procedure as in Example 1, except that the type and amount of the polymer used were changed as shown in Table 1 instead of Polymer 1.

<evaluation>

(display performance evaluation)

GALAXY S4 manufactured by SAMSUNG, which is equipped with an organic EL display element (organic EL display panel), was disassembled, and the circular polarizing plate was peeled off.

Next, on the organic EL display element, a 3% by mass solution (solvent ratio: water/methanol = 75/25) of PVA203 (manufactured by Kuraray Co., Ltd.) was applied by spin coating, and then the organic EL display element having the obtained coating film. was prebaked at 100°C for 2 minutes on a hot plate to volatilize the solvent in the coating film, thereby forming a PVA layer with a film thickness of 0.5 µm.

Moreover, when forming the said PVA layer, the tape was affixed so that the metal electrode connected to the drive element of organic electroluminescent display element might be covered, the said process was performed, and the tape was peeled after prebaking. By this treatment, the PVA layer was not formed on the metal electrode.

Rubbing treatment was performed in the longitudinal direction of the PVA layer.

Next, with respect to the rubbed PVA layer, each composition of Examples and Comparative Examples was spin-coated to a thickness of 1.0 μm, and heat treatment was performed at 90° C. for 120 seconds using a hot plate. Subsequently, a part of the coating film was exposed to light at 90°C at 100 mJ/cm ² (irradiance: 20 mW/cm ² , i-line). At that time, the portion of the metal electrode (connection terminal) connected to the driving element was prevented from being irradiated with light using a photomask.

Then, using an alkaline developing solution (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH)), the coating film was subjected to a developing treatment at 23 ° C. for 60 seconds, and then rinsed with ultrapure water for 1 minute. A metal electrode that was not irradiated with light After removing the coating film located on top of the rinsing, heat treatment was performed in an oven at 150° C. for 30 minutes as a post-bake treatment to form a phase contrast film on the organic light emitting layer of the organic EL display element. In addition, the in-plane retardation of the retardation film formed in each example at a wavelength of 550 nm was 125 nm.

A polarizer was bonded onto the obtained retardation film so that the angle between the in-plane slow axis of the retardation film and the absorption axis of the polarizer was 45°, and an organic EL display device was fabricated.

Visibility was evaluated for the produced organic EL display device in a bright room with an illuminance of 200 lux. Image display (black display) was performed on the organic EL display device, and image sharpness and cloudiness were observed when a fluorescent lamp was illuminated from the front, and evaluated according to the following criteria. The results are shown in Table 1. In practice, it is necessary to be "A" or "B".

A: Cloudiness is not recognized at all, and the image is clear.

B: Cloudiness was partially visually recognized, and a part of the image was slightly blurred.

C: Cloudiness was slightly visually recognized as a whole, and the image was slightly blurred.

D: White turbidity was clearly recognized as a whole, and the image was blurry.

(Drug tolerance evaluation)

After spin-coating a 3% by mass solution (solvent ratio: water/methanol = 75/25) of PVA203 (Kuraray Co., Ltd.) on a glass substrate (10 cm × 10 cm × 0.5 mm, manufactured by Corning, Eagle XG), The glass substrate having the obtained coating film was prebaked at 100°C for 2 minutes on a hot plate, the solvent in the coating film was volatilized, and a PVA layer having a film thickness of 0.5 µm was formed.

Rubbing treatment was performed in the longitudinal direction of the PVA layer.

Next, with respect to the rubbed PVA layer, each composition of Examples and Comparative Examples was spin-coated to a thickness of 1.0 μm, and heat treatment was performed at 90° C. for 120 seconds using a hot plate. Subsequently, the entire surface of the coating film was exposed at 90°C to 100 mJ/cm ² (irradiance: 20 mW/cm ² , i-line), and then the substrate was heated in an oven at 150°C for 30 minutes to obtain a phase contrast film.

The film thickness (T ¹ ) of the obtained retardation film was measured. Then, after immersing the substrate on which the retardation film was formed in a 60°C dimethyl sulfoxide:monoethanolamine=7:3 solution for 10 minutes, the film thickness (t ¹ ) of the retardation film after immersion was measured, and the film thickness by immersion was measured. The rate of change {|t ¹ -T ¹ |/T ¹ }×100 [%] was calculated and evaluated according to the following criteria. The results are shown in Table 1. The calculated numerical value is so preferable that it is small, and A and B are levels with no problem in practical use.

A: Less than 4%

B: 4% or more and less than 8%

C: 8% or more and less than 12%

D: 12% or more

The column "hydrophilic group" in Table 1 corresponds to "A" when the polymer has a hydrophilic group and "B" when it does not have a hydrophilic group.

The column "crosslinkable group" in Table 1 corresponds to "A" when the polymer has a crosslinkable group and "B" when it does not have a crosslinkable group.

The "mesogenic group" column in Table 1 corresponds to "A" when the polymer has a mesogen group and "B" when it does not have a mesogen group.

In Table 1, "-" in the "display performance" column and the "drug resistance" column indicates that the composition used did not have developability, so that a retardation film could not be formed at a predetermined position, so the evaluation was not performed. intend to

[Table 1]

As shown in Table 1, it was confirmed that a phase contrast film can be formed at a predetermined position by using the composition of the present invention.

From the comparison of Examples 1 to 3, it was confirmed that the drug resistance is further improved when the crosslinkable group and the hydrophilic group can react (Examples 1 and 2).

<Example 5>

GALAXY S4 manufactured by SAMSUNG, which is equipped with an organic EL display element (organic EL display panel), was disassembled, and the circularly polarizing plate was peeled off.

Next, on the organic EL display element, the following composition for forming a photo-alignment film was applied to a dry film thickness of about 100 nm, and dried at 80°C for 2 minutes. Next, the obtained coating film was irradiated with polarized UV (ultraviolet light) (100 mW/cm ² ) at an intensity of 100 mW/cm ² . Further, exposure was performed through a mask so that light was not irradiated to the metal electrode region connected to the drive element of the organic EL display element during UV exposure.

(Composition for forming photo-alignment layer)

30 parts by mass of the following photo-alignable polymer

10 parts by mass of pentaerythritol tetraacrylate

Photopolymerization initiator (Irgacure 907, manufactured by BASF) 5 parts by mass

2250 parts by mass of toluene

・Photo-alignment polymer (poly[4-methoxycinnamate-5-norbornene], Mw=150,000)

[Formula 12]

In addition, the uncured portion was removed with a solvent. By this process, the coating film was not formed on the metal electrode.

After that, in the same manner as in Example 1, an organic EL display device was produced by applying the composition. The in-plane retardation of the produced retardation film at a wavelength of 550 nm was 125 nm. In addition, the obtained retardation film exhibited the same chemical resistance as Example 1.

In addition, the coating film did not remain on the metal electrode.

<Example 6>

In Example 5, the same as in Example 5, except that polarized UV exposure was performed through a polarized mask designed so that polarized light having a polarization direction different from each other by 45° is emitted to adjacent areas in the form of a 2 mm wide stripe as the alignment treatment. Thus, an organic EL display device was fabricated. In addition, the polarizer was bonded so that its absorption axis formed an angle of 45° with the slow axis direction of one of the two orientation regions in which the retardation film was different.

The chemical resistance of the obtained retardation film was "A" as in Example 5.

In addition, with respect to the organic EL display device produced, when the organic EL display device was set to black display in a bright room with an illumination intensity of 200 lux and a fluorescent lamp was illuminated from the front, a light-dark pattern was observed in the form of a stripe of 2 mm width, incident on the bright part. A light was faintly reflected. That is, it was shown that the phase contrast film was patterned with a predetermined phase difference.

In addition, the coating film did not remain on the metal electrode.

In this embodiment, a specific example is shown with a simple stripe-like pattern, but it is clear that, for example, if a design having a visual aid effect is implemented instead of the stripe-like pattern, the display performance based on the user's experience can be improved.

<Example 7>

An organic EL display device was produced in the same manner as in Example 1 by adding a chiral agent to the composition of Example 1. The chemical resistance of the obtained retardation film was "A" as in Example 1.

The obtained retardation layer exhibited a blue reflection color from the front. The originally peeled circular polarizing plate was bonded back in the original direction, and then the luminance during blue display was measured in a dark room. A 10% luminance improvement effect with respect to the original luminance was confirmed.

In addition, the coating film did not remain on the metal electrode.

10 Mother board
12 organic light emitting layer
14 connection terminal
16, 32 organic EL display elements
20, 30 substrate
22 adhesive layer
24 40 phase shield
34 coating
36 Exposure part
38 Unexposed Miners

Claims (12)

A polymer having a hydrophilic group, a crosslinkable group, and a mesogenic group;
Including polymeric compounds,
The polymer includes a repeating unit having the crosslinkable group and the mesogen group and a repeating unit having the hydrophilic group,
The content of the repeating unit having a hydrophilic group is 10 to 30% by mass based on the mass (100% by mass) of all repeating units in the polymer,
The crosslinkable group is a group selected from the group consisting of an oxetanyl group and an epoxy group,
The hydrophilic group is a group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group,
The hydrophilic group and the crosslinkable group can react by heating,
A composition for forming a retardation film disposed on an organic electroluminescence display device. delete delete delete delete The method of claim 1,
A composition further comprising a polymerization initiator. The method of claim 1,
The composition in which the said polymeric compound is a polymeric liquid crystal compound. A phase contrast film for an organic electroluminescence display element formed by using the composition according to claim 1. The method of claim 8,
A λ/4 plate or λ/2 plate phase contrast film for organic electroluminescence display elements. The method of claim 8,
A phase contrast film for organic electroluminescence display elements exhibiting reverse wavelength dispersion. an organic electroluminescence display element;
An organic electroluminescence display device comprising the organic electroluminescence display element retardation film according to claim 8 disposed on the organic electroluminescence display element. forming a coating film on a substrate on which an organic electroluminescence display element is disposed, using the composition according to claim 1;
a step of orienting the mesogen groups in the coating film;
A step of exposing a part of the coating film;
A method for producing a retardation film for an organic electro luminescence display element, comprising a step of developing the exposed coating film and forming a retardation film for an organic electro luminescence display element on the organic electro luminescence display element.

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