JP5747515B2 - Composition for controlling alignment of organic EL illuminant, organic EL illuminant alignment control film, organic EL element and method for producing the same - Google Patents

Description

  The present invention relates to an organic EL light emitter alignment control composition suitable for forming a film capable of controlling the orientation of an organic EL light emitter, an organic EL light emitter alignment control film formed thereby, and this organic EL light emitter alignment control The present invention relates to an organic EL element having a film and a method for manufacturing the same.

  Organic EL (electroluminescence) elements, inorganic EL elements, semiconductor LEDs, plasma displays, and the like have been developed as devices that emit light from the elements themselves. The development of display devices that take advantage of the characteristics of each light-emitting element is underway. In particular, organic EL elements using organic EL emitters, which are light-emitting organic compounds, can be easily reduced in thickness and have low power consumption. It is attracting attention because of its excellent brightness and video display function.

  As one application example of such an organic EL element, an attempt has been made to use it as a backlight of a liquid crystal display element. The liquid crystal itself does not emit light, but displays image information by using a backlight that emits natural light including a broad wavelength. In order to suppress the power consumption as a whole while improving the image display function of the liquid crystal display element, it is required to effectively use light from the backlight.

  The liquid crystal display element displays image information by adjusting light transmitted through the polarizing plate by voltage control to the liquid crystal cell. A polarizing plate has a property of passing only polarized light in a predetermined direction, whereas light emitted from a normal backlight is non-polarized light, so a part of the light emitted from the backlight is polarized on the backlight side. It will be blocked by a board. In such a situation, it cannot be said that the light from the backlight is effectively used, and as a result, this is one of the causes for increasing the power consumption of the liquid crystal display element. In general, in an organic EL element, light is emitted by the combination of electrons from the cathode and holes from the anode in the light emitting layer, and the light extracted thereby is unpolarized, so the organic EL element was used as it is. Therefore, it cannot be used more efficiently as backlight.

  Thus, a technique has been proposed in which light polarized in one direction is emitted from the backlight itself, thereby reducing the proportion of light blocked by the polarizing plate and effectively using much light. Based on this idea, as an example of applying the organic EL element to the polarized light-emitting backlight as described above, an organic EL element has been developed that emits polarized light from the light emission stage by uniaxially aligning the light emitter layer. .

  According to the conventional technology for aligning a light emitter layer, a compound constituting the light emitter layer is uniaxially oriented by forming the light emitter layer on the alignment film. Specifically, a film subjected to rubbing treatment is used as an alignment film, and a light-emitting body is formed on the alignment film, whereby the light-emitting body is uniaxially aligned (see, for example, JP-A-11-204261). By using such an organic EL element that emits polarized light as a light source, light loss due to the polarizing plate as described above is reduced. However, when the rubbing treatment is performed, the surface of the film is physically scraped, so that the film and other layers may be damaged. Furthermore, when rubbing is performed, fine dust is generated, and there is a possibility that a short circuit may occur due to the dust. From the above points, the rubbing method has a limit in producing a highly reliable organic EL element.

  Therefore, as a technique for spontaneously orienting the phosphor layer instead of rubbing treatment, the phosphor layer includes a photo-alignment compound that is at least partially uniaxially aligned when irradiated with light, and an organic compound that emits light. A configured organic EL element has been proposed (see, for example, JP 2009-239180 A). Although this organic EL element does not cause the above-described problems when the rubbing treatment is performed, the alignment of the light emitting layer by light irradiation is not easy compared to the case where the alignment film subjected to the rubbing treatment is used, and the alignment of the light emitting layer. Requires a considerable amount of light irradiation. In addition, the luminous efficiency is reduced with respect to the heat load during manufacture and use as compared to before the heat load.

  In view of such circumstances, the light emission efficiency is stable due to high heat resistance, and the anisotropic orientation of the organic EL light-emitting body is induced at a high level, and the light emission efficiency of polarized light (hereinafter simply referred to as “polarized light emission efficiency”). Development of an organic EL light emitter alignment control film capable of increasing the above) and an organic EL light emitter alignment control composition having good photoalignment sensitivity capable of forming the organic EL light emitter alignment control film is desired.

Japanese Patent Laid-Open No. 11-204261 JP 2009-239180 A

  The present invention has been made based on the circumstances as described above, and its purpose is that the sensitivity of photo-alignment is good, the light emission efficiency is stable due to high heat resistance, and the organic EL light emitter is anisotropic. Organic EL light emitter alignment control film capable of increasing the light emission efficiency of polarized light by inducing alignment at a high level, organic EL light emitter alignment control composition capable of forming the same, and organic EL light emitter alignment control film It is providing an organic electroluminescent element provided with these, and its manufacturing method.

The invention made to solve the above problems is
[A] A composition for controlling the alignment of an organic EL light-emitting material containing a compound having a photoalignable group containing a cinnamic acid structure (hereinafter also referred to as “[A] compound” or “photoalignable compound”).

  Since the composition for organic EL light emitter alignment control contains a compound having a photoalignable group containing a [A] cinnamic acid structure, when forming an organic EL light emitter alignment control film using this, Good light alignment sensitivity can reduce the amount of light irradiation required for alignment of the photo-alignable group, thereby increasing the production efficiency of the organic EL element. In addition, the [A] compound anisotropically oriented in the organic EL light emitter alignment control film formed using the organic EL light emitter alignment control composition is anisotropic at a high level of the organic EL light emitter. Orientation is enabled, and as a result, excellent polarized light emission efficiency in the organic EL element can be achieved.

  [A] The compound is preferably a polyorganosiloxane compound. According to the composition for controlling alignment of organic EL light-emitting material, the [A] compound is a polyorganosiloxane compound, that is, by adopting polyorganosiloxane as the main chain structure, the thermal orientation control film obtained It has high stability and chemical stability and high heat resistance, so that the initial luminous efficiency can be maintained at a high rate for a long time even after heat load.

（式（１）中、Ｒ^１は、フェニレン基、ビフェニレン基、ターフェニレン基又はシクロヘキシレン基であり、このフェニレン、ビフェニレン基、ターフェニレン基又はシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０のアルキル基、置換基としてフッ素原子を有していてもよい炭素数１〜１０のアルコキシ基、フッ素原子又はシアノ基で置換されてもよい。Ｒ^２は、単結合、炭素数１〜３のアルキレン基、酸素原子、硫黄原子、−ＣＨ＝ＣＨ−、−ＮＨ−又は−ＣＯＯ−である。ａは、０〜３の整数であり、ａが２以上の場合、Ｒ^１及びＲ^２はそれぞれ同じでも異なっていてもよい。Ｒ^３はフッ素原子又はシアノ基であり、ｂは０〜４の整数である。
式（２）中、Ｒ^４は、フェニレン基又はシクロヘキシレン基であり、このフェニレン基又はシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０の鎖状又は環状のアルキル基、炭素数１〜１０の鎖状又は環状のアルコキシ基、フッ素原子又はシアノ基で置換されてもよい。Ｒ^５は、単結合、炭素数１〜３のアルキレン基、酸素原子、硫黄原子又は−ＮＨ−である。ｃは、１〜３の整数であり、ｃが２以上の場合、Ｒ^４及びＲ^５はそれぞれ同じでも異なっていてもよい。Ｒ^６は、フッ素原子又はシアノ基であり、ｄは０〜４の整数である。Ｒ^７は、酸素原子、−ＣＯＯ−＊又は−ＯＣＯ−＊（ただし、以上において「＊」を付した結合手がＲ^８と結合する）である。Ｒ^８は、２価の芳香族基、２価の脂環式基、２価の複素環式基又は２価の縮合環式基である。Ｒ^９は、単結合、−ＯＣＯ−（ＣＨ_２）_ｆ−＊又は−Ｏ（ＣＨ_２）_ｇ−＊（ただし、以上において「＊」を付した結合手がカルボキシル基と結合する）である。ｆ及びｇはそれぞれ１〜１０の整数であり、ｅは０〜３の整数である。） In the composition for organic EL light emitter alignment control, the photo-alignable group containing the cinnamic acid structure is derived from a group represented by the following formula (1) and a compound represented by (2). It is preferable that it is at least one selected from the group consisting of groups (hereinafter, one or both of a compound represented by the following formula (1) and a compound represented by the following formula (2) are simply “specific cinnamon”. Also referred to as “acid derivative”).

(In the formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group, and a part or all of the hydrogen atoms of the phenylene, biphenylene group, terphenylene group or cyclohexylene group are The alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom as a substituent, a fluorine atom or a cyano group may be substituted, R ² is a single bond, carbon An alkylene group having a number of 1 to 3, an oxygen atom, a sulfur atom, —CH═CH—, —NH—, or —COO—, a is an integer of 0 to 3, and when a is 2 or more, R ¹ And R ² may be the same or different, R ³ is a fluorine atom or a cyano group, and b is an integer of 0 to 4.
In the formula (2), R ⁴ is a phenylene group or a cyclohexylene group, and part or all of the hydrogen atoms of the phenylene group or cyclohexylene group are a linear or cyclic alkyl group having 1 to 10 carbon atoms, It may be substituted with a linear or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group. R ⁵ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or —NH—. c is an integer of 1 to 3, and when c is 2 or more, R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group, and d is an integer of 0 to 4. R ⁷ is an oxygen atom, —COO— * or —OCO— * (in the above, a bond marked with “*” is bonded to R ⁸ ). R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — * (provided that a bond marked with “*” above binds to a carboxyl group). f and g are each an integer of 1 to 10, and e is an integer of 0 to 3. )

  By using the group derived from the specific cinnamic acid derivative as the photo-alignable group containing the cinnamic acid structure, the anisotropy imparting performance to the organic EL light-emitting body, that is, the alignment performance is further enhanced. It becomes easy to define the orientation (anisotropic orientation), and the polarized light emission efficiency of the organic EL light emitting layer can be further improved.

  In the composition for controlling the alignment of organic EL light emitters, the [A] compound is composed of a polyorganosiloxane containing a monovalent organic group having an epoxy group, a hydrolyzate thereof, and a condensate of the hydrolyzate. Selected from the group consisting of at least one selected (hereinafter also simply referred to as “polyorganosiloxane having an epoxy group”), a compound represented by the above formula (1) and a compound represented by the above formula (2) The reaction product with at least one selected from the above is preferable. In the organic EL phosphor alignment control composition, by using the reactivity between the polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, the polyorganosiloxane as the main chain has a photoalignment property. Side chain groups derived from cinnamic acid derivatives can be easily introduced.

（式（Ｘ_１−１）中、Ａは酸素原子又は単結合である。ｈは１〜３の整数であり、ｉは０〜６の整数である。ただし、ｉが０の場合、Ａは単結合である。
式（Ｘ_１−２）中、ｊは１〜６の整数である。
式（Ｘ_１−１）及び（Ｘ_１−２）中、「＊」は、それぞれ結合手であることを示す。） In the organic EL light emitter orientation control composition, the monovalent organic group having an epoxy group is preferably represented by the following formula (X ₁ -1) or (X ₁ -2).

(In the formula (X ₁ -1), A is an oxygen atom or a single bond. H is an integer of 1 to 3, i is an integer of 0 to 6. However, when i is 0, A is It is a single bond.
Wherein _(X 1 -2), j is an integer from 1 to 6.
In the formulas (X ₁ -1) and (X ₁ -2), “*” represents a bond. )

By adopting the structure represented by the formula (X ₁ -1) or (X ₁ -2) as the monovalent organic group having the epoxy group, the polyorgano of the composition for controlling the alignment of organic EL light emitters is adopted. It becomes easy to introduce a side chain group derived from the specific cinnamic acid derivative into siloxane.

  The composition for controlling the orientation of organic EL light emitters comprises [B] acetal ester structure of carboxylic acid, ketal ester structure of carboxylic acid, 1-alkylcycloalkyl ester structure of carboxylic acid, and t-butyl ester structure of carboxylic acid. It is preferable to further contain a compound having at least two structures selected from the group (hereinafter also referred to as “[B] compound” or “ester structure-containing compound”). By including such a compound [B] in the composition for controlling the alignment of organic EL light emitter, an acid is generated in a baking step (hereinafter also referred to as “post-bake”) before polarized light irradiation. [A] Crosslinking of the compound can be promoted, and as a result, the heat resistance of the resulting organic EL light-emitting alignment control film can be improved.

  The organic EL light emitter alignment control film of the present invention is formed of the organic EL light emitter alignment control composition. As a result, the organic EL phosphor alignment control film exhibits excellent luminous efficiency stability due to high heat resistance even after thermal load, and the uniaxial alignment of the organic EL phosphor can be easily defined by the photo-alignment group. Excellent polarized light emission efficiency in the EL light emitting layer can be exhibited.

  The organic EL element of the present invention is formed on an anode electrode formed on a substrate, the organic EL light emitter alignment control film formed so as to cover the anode electrode, and the organic EL light emitter alignment control film. The organic EL light emitting layer and a cathode electrode formed on the organic EL light emitting layer. Since the organic EL element employs the organic EL light emitter alignment control film as an alignment control film for the organic EL light emitter layer, the organic EL element exhibits excellent photoalignment sensitivity and light for forming the alignment control film. While being able to reduce an irradiation amount, the polarized light emission efficiency in an organic electroluminescent light emitting layer can be improved. Moreover, since the heat resistance of the organic EL light emitter alignment control film is high, the original light emission efficiency can be maintained for a long time even after heat load.

  The method for producing an organic EL device of the present invention includes a step of forming a coating film using the composition for controlling the alignment of an organic EL light emitter so as to cover an anode electrode formed on a substrate, and linearly polarized light on the coating film. Forming an organic EL light emitter alignment control film, forming an organic EL light emitter layer on the organic EL light emitter alignment control film, and forming a cathode electrode on the organic EL light emitter layer The process of carrying out. By employ | adopting the manufacturing method of the said organic EL element, the said organic EL element can be manufactured efficiently and simply.

  As described above, according to the composition for organic EL light emitter alignment control, the organic EL light emitter alignment control film, the organic EL element, and the manufacturing method thereof according to the present invention, good photoalignment sensitivity can be achieved. While realizing luminous efficiency stability due to heat resistance, the organic EL luminous body can be anisotropically oriented at a high level to exhibit excellent polarized luminous efficiency.

It is typical sectional drawing which shows an example of the organic EL element of this invention.

  Since the composition for controlling the alignment of organic EL phosphor of the present invention contains a compound having a photo-alignable group containing [A] a cinnamic acid structure, the amount of light irradiation necessary for alignment can be obtained by highly sensitive photo-alignment. Can be reduced. In addition, by using the composition for controlling the alignment of organic EL light emitter, the obtained organic EL light emitter alignment control film exhibits high heat resistance, and thereby can exhibit high light emission efficiency stability after thermal load. . In addition, since this organic EL light emitter alignment control film has excellent photo-orientation properties, it is possible to develop anisotropic orientation at a high level in the organic EL light emitter layer, and to improve the polarization emission efficiency of the organic EL element. Can be improved.

  The organic EL light emitter orientation control composition may contain the [A] compound and may contain the [B] compound (ester structure-containing compound) as a suitable component, and other optional components, [A] Polymers other than the compound (hereinafter also simply referred to as “other polymer”), curing agent, curing catalyst, curing accelerator, compound having at least one epoxy group in the molecule (hereinafter simply referred to as “epoxy compound”) And a functional silane compound, a surfactant, a photosensitizing compound, and the like. Hereinafter, the composition for controlling the alignment of the organic EL phosphor will be described.

<[A] component: a compound having a photoalignable group containing a cinnamic acid structure>
[A] A compound has a photo-alignment group. When an organic EL light emitter alignment control film is formed with the composition for controlling organic EL light emitter alignment, the organic EL light emitter alignment control film is irradiated with light having anisotropy such as polarized light on this photo-alignable group. It induces chemical reactions with molecular rearrangement and anisotropy. Anisotropy is imparted to the organic EL light emitter by the change in the molecular structure of the orientation control film accompanied by this anisotropy.

  The photo-alignment group includes a cinnamic acid structure having cinnamic acid or a derivative thereof as a basic skeleton. When the photo-alignable group contains a cinnamic acid structure, it exhibits a dimerization-type anisotropy, exhibits high alignment ability, and facilitates introduction of the photo-alignment group. Cinnamic acid or a derivative thereof may be cis type or trans type as long as it can be dimerized by light irradiation.

The structure of the photoalignable group containing a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton, but it is represented by the compound represented by the above formula (1) and the above formula (2). It is preferably a group derived from at least one of the compounds to be produced (that is, the specific cinnamic acid derivative). In the above formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group, and part or all of the hydrogen atoms of the phenylene, biphenylene group, terphenylene group or cyclohexylene group May be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom as a substituent, a fluorine atom or a cyano group. R ² is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, —CH═CH—, —NH— or —COO—. a is an integer of 0 to 3, and when a is 2 or more, R ¹ and R ² may be the same or different. R ³ is a fluorine atom or a cyano group, and b is an integer of 0 to 4.

  Examples of the compound represented by the above formula (1) include the following.

Among these, R ¹ is preferably an unsubstituted phenylene group or a phenylene group substituted with a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and R ² is a single bond, an oxygen atom, or —CH═CH—. Some are preferred. b is preferably 0 to 1, and when a is 1 to 3, b is particularly preferably 0.

In said formula (2), R < ⁴ > is a phenylene group or a cyclohexylene group, and a part or all of the hydrogen atom of this phenylene group or a cyclohexylene group is a C1-C10 linear or cyclic alkyl group. May be substituted with a linear or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom, or a cyano group. R ⁵ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or —NH—. c is an integer of 1 to 3, and when c is 2 or more, R ⁴ and R ⁵ may be the same or different. R ⁶ is a fluorine atom or a cyano group, and d is an integer of 0 to 4. R ⁷ is an oxygen atom, —COO— * or —OCO— * (in the above, a bond marked with “*” is bonded to R ⁸ ). R ⁸ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. R ⁹ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — * (provided that a bond marked with “*” above binds to a carboxyl group). f and g are each an integer of 1 to 10, and e is an integer of 0 to 3.

  Examples of the compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-4).

（式中、Ｑは、炭素数１〜１０の鎖状又は環状のアルキル基、炭素数１〜１０の鎖状又は環状のアルコキシ基、フッ素原子又はシアノ基であり、ｆは式（２）と同義である。）

(In the formula, Q is a linear or cyclic alkyl group having 1 to 10 carbon atoms, a linear or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom, or a cyano group, and f is a formula (2) Synonymous.)

<Synthesis of specific cinnamic acid derivatives>
The procedure for synthesizing the specific cinnamic acid derivative is not particularly limited, and can be performed by combining conventionally known methods. Typical synthesis procedures include, for example, (1) reacting a compound having a benzene ring skeleton substituted with a halogen atom under basic conditions with acrylic acid in the presence of a transition metal catalyst to produce a specific cinnamic acid derivative. (2) A reaction in which cinnamic acid in which a hydrogen atom of a benzene ring is substituted with a halogen atom and a compound having a benzene ring skeleton in which the halogen atom is substituted are reacted in the presence of a transition metal catalyst under basic conditions. The method etc. which make a specific cinnamic acid derivative are illustrated. However, the synthesis procedure of the specific cinnamic acid derivative is not limited to these.

  [A] The compound is not particularly limited as long as it has a photoalignable group containing a cinnamic acid structure, but is preferably a polymer having a photoalignable group containing a cinnamic acid structure in the side chain, such as polyorganosiloxane, polyimide, Polyamic acids, polyacrylates, polymethacrylates, poly (styrene-phenylmaleimide) derivatives, cellulose derivatives, polyesters, polyamides, polystyrene derivatives and polyamic acid esters having a main chain structure are more preferred in terms of electrical properties, and light resistance In view of the above, a polyorganosiloxane having a main chain structure is more preferable.

  [A] The compound having a polyorganosiloxane as the main chain structure (polyorganosiloxane compound) is selected from the group consisting of polyorganosiloxane as the main chain, a hydrolyzate thereof, and a condensate of the hydrolyzate. It has a structure in which the photo-alignment group is introduced as a side chain in a portion derived from at least one kind. When the compound [A] is a polyorganosiloxane compound, the photoalignment group and the polyorganosiloxane compound can improve the sensitivity of photoalignment and realize a low light irradiation amount. At the same time, since polyorganosiloxane is adopted as the main chain, the organic EL phosphor alignment control film formed from the organic EL phosphor alignment control composition has excellent chemical stability and thermal stability. And exhibiting high heat resistance, the luminous efficiency can be maintained over a long period of time even after a thermal load.

<Part derived from at least one selected from the group consisting of polyorganosiloxane, a hydrolyzate thereof and a condensate of the hydrolyzate>
[A] When the compound is a polyorganosiloxane compound, a portion derived from at least one selected from the group consisting of a polyorganosiloxane contained in the main chain, a hydrolyzate thereof, and a condensate of the hydrolyzate As long as it has a portion derived from a structure capable of introducing the photo-alignment group into itself, it is not particularly limited. The [A] compound, which is a polyorganosiloxane compound, includes a portion derived from at least one selected from the group consisting of such polyorganosiloxane, a hydrolyzate thereof, and a condensate of the hydrolyzate, and the photo-alignment. And a group derived from a compound exhibiting properties.

  Examples of the structure into which the photoalignable group can be introduced include a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a mercapto group, an ester group, and an amide group. Among these, an epoxy group is preferable in consideration of ease of introduction and preparation.

  [A] The compound is preferably a reaction product of a polyorganosiloxane having an epoxy group and a compound represented by the above formula (1) and / or (2). In the organic EL phosphor alignment control composition, by using the reactivity between the polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, the polyorganosiloxane as the main chain has a photoalignment property. Groups derived from cinnamic acid derivatives can be easily introduced.

<Polyorganosiloxane having epoxy group>
The polyorganosiloxane having an epoxy group used in the composition for controlling alignment of organic EL light emitters is not particularly limited as long as a monovalent organic group having an epoxy group as a side chain is introduced into the polyorganosiloxane. The polyorganosiloxane having an epoxy group is at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (3), a hydrolyzate thereof, and a condensate of the hydrolyzate. It is preferable that

（式（３）中、Ｘ^１はエポキシ基を有する１価の有機基であり、Ｙ^１は水酸基、炭素数１〜１０のアルコキシ基、炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基である。）

(In the formula (3), ^{X 1} is a monovalent organic group having an epoxy group, ^{Y 1} is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, 6 to 20 alkyl group carbon atoms or 1 to 20 carbon atoms Of the aryl group.)

  In addition, the hydrolyzate of polyorganosiloxane which has a repeating unit represented by the said Formula (3), or its condensate is represented not only by the hydrolysis condensate of the polyorganosiloxane but the said Formula (3). In the process in which polyorganosiloxane is produced by hydrolysis and condensation of repeating units, the polyorganosiloxane obtained by branching or crosslinking of the main chain has a repeating unit represented by the above formula (3). It is a concept including a decomposed product or a condensate thereof.

X ¹ in the above formula (3) is not particularly limited as long as it is a monovalent organic group having an epoxy group, and examples thereof include a group containing a glycidyl group, a glycidyloxy group, and an epoxycyclohexyl group. The monovalent organic group having an epoxy group (that is, X ¹ ) is preferably represented by the above formula (X ₁ -1) or (X ₁ -2). Furthermore, among groups represented by the above formula (X ₁ -1) or (X ₁ -2), the following formula (X ₁ -1-1) or (X ₁ -2-1)

（上記式中、「＊」は結合手であることを示す。）
で表される基が好ましい。

(In the above formula, “*” indicates a bond.)
The group represented by these is preferable.

In Y ¹ in the above formula (3), as an alkoxy group having 1 to 10 carbon atoms, for example, a methoxy group, an ethoxy group, etc .; as an alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, or an n-propyl group N-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group N-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc .; as the aryl group having 6 to 20 carbon atoms, for example, phenyl Each group can be mentioned.

  The polyorganosiloxane having an epoxy group preferably has a polystyrene-equivalent mass average molecular weight measured by gel permeation chromatography (GPC) of 500 to 100,000, preferably 1,000 to 10,000. More preferably, it is preferably 1,000 to 5,000.

  Such polyorganosiloxane having an epoxy group is preferably a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst. Can be synthesized by hydrolysis or hydrolysis / condensation.

  Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy A silane etc. can be mentioned.

Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, and trichlorosilane. Methoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluoro Tri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyl Triethoxysilane, methyl tri -n- propoxysilane, methyltri -i- propoxysilane, methyltri -n- butoxysilane, methyltri -sec- butoxysilane, 2- (trifluoromethyl) ethyl trichlorosilane,
2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxy Silane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro- n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ) Ethyltri-i-propoxysilane, 2- (par Fluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro- n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane,

  2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i- Propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meta Acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propoxysilane, 3- (meth) acryloxypropyltri-n-butoxy Silane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercaptomethyltrimethoxysilane,

  Mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltri Chlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane, allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyl Triethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-se -Butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane,

  (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (Methyl) (3-mercaptopropyl) dichlorosilane, (methyl) (3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercapto Propyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i-propoxysilane, (methyl) (3-mercaptopropyl) di-n -Butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl ) (Vinyl) di-n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane,

  (Methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec -Butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chloro Dimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytri Tylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, In addition to silane compounds having one silicon atom such as (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl) diphenylsilane,

  Product names such as KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X -21-5848, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22 -176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672 , X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-10 3, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (manufactured by Shin-Etsu Chemical Co., Ltd.); glass resin (manufactured by Showa Denko KK); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dow Corning Co., Ltd.); FZ3711, FZ3722 (above, manufactured by Nihon Unicar Co., Ltd.); DMS-S1 , DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD -0332, PDS-1615, PDS-9931, XMS-5025 (above, manufactured by Chisso Corporation); Methyl silicate MS51, Methyl silicate MS56 (above, manufactured by Mitsubishi Chemical Corporation); Ethyl silicate 28, Ethyl silicate 40, Examples include partial condensates such as ethyl silicate 48 (manufactured by Colcoat Co., Ltd.); GR100, GR650, GR908, GR950 (manufactured by Showa Denko Co., Ltd.).

  Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-trimethylsilane, from the viewpoint of the orientation and chemical stability of the organic EL phosphor alignment control film obtained. (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysila It is preferred.

  The polyorganosiloxane having an epoxy group used in the present invention suppresses unintended side reactions caused by excessive introduction of epoxy groups while introducing a sufficient amount of side chains having photo-alignment properties. In addition, the epoxy equivalent is preferably 100 to 10,000 g / mol, and more preferably 150 to 1,000 g / mol. Therefore, in synthesizing a polyorganosiloxane having an epoxy group, the use ratio of the silane compound having an epoxy group and another silane compound is adjusted so that the obtained polyorganosiloxane epoxy equivalent is in the above range. It is preferable to set.

  Specifically, such other silane compound is preferably used in an amount of 0 to 50% by mass, preferably 5 to 30% by mass, based on the total of the polyorganosiloxane having an epoxy group and the other silane compound. More preferred.

  Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include hydrocarbon compounds, ketone compounds, ester compounds, ether compounds, alcohol compounds, and the like.

  Examples of the hydrocarbon compound include toluene and xylene; Examples of the ketone compound include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; Examples of the ester compound include ethyl acetate and acetic acid. n-butyl, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; Examples of the ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran and dioxane; Is, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ethylene glycol mono -n- propyl ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether, can be mentioned, respectively. Of these, water-insoluble ones are preferred. These organic solvents can be used alone or in admixture of two or more.

  The amount of the organic solvent used is preferably 10 to 10,000 parts by mass, and more preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the total silane compounds. Moreover, the amount of water used in producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on the total silane compound.

  As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

  Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Examples thereof include tertiary organic amines such as diazabicycloundecene; quaternary organic ammonium salts such as tetramethylammonium hydroxide, and the like. Of these organic bases, a tertiary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; Quaternary organic ammonium salts such as methylammonium hydroxide are preferred.

  As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing side reactions such as ring opening of the epoxy group, resulting in stable production. It is preferable because of its excellent properties. Moreover, the composition for organic EL light emitter alignment control of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a specific cinnamic acid derivative, This is advantageous because of excellent storage stability.

  The reason is that, as pointed out in Chemical Reviews, Vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in a hydrolysis or condensation reaction, a random structure, a ladder structure or a cage structure is used. It is presumed that a structure is formed and a polyorganosiloxane having a low content of silanol groups is obtained. Since the content ratio of silanol groups is small, the condensation reaction between silanol groups is suppressed, and furthermore, when the composition for controlling the orientation of organic EL light emitters of the present invention contains other polymers described below, Since the condensation reaction between the silanol group and the other polymer is suppressed, it is presumed that the storage stability is excellent.

  As the catalyst, an organic base is particularly preferable. The amount of organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and can be set appropriately. As a specific usage-amount of an organic base, it becomes like this. Preferably it is 0.01-3 times mole with respect to all the silane compounds, More preferably, it is 0.05-1 times mole.

  Hydrolysis or hydrolysis / condensation reaction when producing polyorganosiloxane having an epoxy group is carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, and dissolving the solution in an organic base. And it is preferable to carry out by mixing with water and heating with, for example, an oil bath.

  During the hydrolysis / condensation reaction, the heating temperature of the oil bath is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.

  After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this cleaning, it is preferable to perform cleaning with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by mass in view of facilitating the cleaning operation. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the target is removed by removing the solvent. A polyorganosiloxane having an epoxy group can be obtained.

  In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

  The compound [A] is a part derived from a hydrolyzate produced by hydrolysis of a polyorganosiloxane itself having an epoxy group, or a part derived from a hydrolysis condensate obtained by hydrolytic condensation of polyorganosiloxanes having an epoxy group. May be included. These hydrolyzates and hydrolysis condensates which are constituent materials of the part can also be prepared in the same manner as the hydrolysis or condensation conditions of polyorganosiloxane having an epoxy group.

<Synthesis of [A] Compound>
When the [A] compound used in the present invention is a polyorganosiloxane compound, for example, a polyorganosiloxane having an epoxy group as described above and a compound represented by the above formula (1) and / or (2) (that is, The specific cinnamic acid derivative) can be synthesized preferably by reacting in the presence of a catalyst.

  Here, the specific cinnamic acid derivative is preferably used in an amount of 0.001 to 10 mol, more preferably 0.01 to 5 mol, still more preferably 0.05 to 2 mol based on 1 mol of the epoxy group of the polyorganosiloxane. The

  As said catalyst, a well-known compound can be used as what is called a hardening accelerator which accelerates | stimulates reaction with an organic base or an epoxy compound, and an acid anhydride.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
A quaternary organic amine such as tetramethylammonium hydroxide can be used.
Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic ammonium salts such as tetramethylammonium hydroxide Is preferred.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, and 2,4-diamino-6- [2'- An imidazole compound such as an isocyanuric acid adduct of methylimidazolyl- (1 ′)] ethyl-s-triazine;
Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra Phenylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate Such bets quaternary phosphonium salts;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;
An amine salt type latent curing accelerator;
Examples include latent curing accelerators such as high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

  Among these catalysts, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

  The catalyst is used in an amount of preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyorganosiloxane having an epoxy group. .

  The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

  The compound [A] can be synthesized in the presence of an organic solvent as necessary. Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products. The solvent has a solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution), preferably 0.1% by mass to 70% by mass, more preferably 5% by mass to 50% by mass. % Is used in an amount of less than%.

  The compound [A] of the present invention can be obtained by introducing a structure derived from a specific cinnamic acid derivative into the polyorganosiloxane having an epoxy group by ring-opening addition of the carboxyl group of the specific cinnamic acid derivative to the epoxy. . This production method is simple and is a very suitable method in that the introduction rate of the structure derived from the specific cinnamic acid derivative can be increased.

  In the present invention, a part of the specific cinnamic acid derivative may be replaced with a compound represented by the following formula (4) as long as the effects of the present invention are not impaired. In this case, the compound [A] is synthesized by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific cinnamic acid derivative and a compound represented by the following formula (4).

R ¹⁰ in the above formula (4) is an alkyl group or an alkoxy group in which part or all of the hydrogen atoms may be substituted with fluorine, preferably an alkyl group or an alkoxy group having 8 to 20 carbon atoms, or It is a C4-C21 fluoroalkyl group or fluoroalkoxy group. R ¹¹ is a single bond, a cycloalkylene group or an arylene group, preferably a single bond, a 1,4-cyclohexylene group or a 1,4-phenylene group. R ¹² is an organic acid group, preferably a carboxyl group.

  Preferable examples of the compound represented by the above formula (4) include, for example, compounds represented by any of the following formulas (4-1) to (4-3).

  The compound represented by the formula (4) can deactivate the active site of the [A] compound and contribute to an improvement in the stability of the composition for controlling the alignment of an organic EL light-emitting body. In the present invention, when the compound represented by the above formula (4) is used together with the specific cinnamic acid derivative, the total use ratio of the specific cinnamic acid derivative and the compound represented by the above formula (4) is the polyorganosiloxane. Preferably it is 0.001-1.5 mol with respect to 1 mol of epoxy groups to have, More preferably, it is 0.01-1 mol, More preferably, it is 0.05-0.9 mol. In this case, the compound represented by the formula (4) is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total with the specific cinnamic acid derivative. When the use ratio of the compound represented by the above formula (4) exceeds 50 mol%, there is a possibility that the orientation in the organic EL light emitting device orientation control film is deteriorated.

  The production method when the compound [A] is a polymer other than the polyorganosiloxane compound includes a known polymer having a structure capable of introducing a photoalignable group, cinnamic acid and cinnamic acid derivatives (the above-mentioned specific cinnamic acid Derivatives, cinnamate chlorides, etc.) can be reacted. Examples of the structure into which the photoalignable group can be introduced include a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a mercapto group, an ester group, and an amide group.

  The mass average molecular weight in terms of styrene by gel permeation chromatography of the [A] compound thus obtained is not particularly limited, but is preferably 1,000 to 20,000, preferably 3,000 to 15, More preferably, it is 000. By being in such a molecular weight range, it is possible to ensure good orientation and thermal stability of the organic EL light emitter orientation control film.

<[B] component: ester structure-containing compound>
By including the [B] ester structure-containing compound, the organic EL phosphor alignment control composition can form an organic EL phosphor alignment control film having excellent heat resistance and light resistance, and the organic EL phosphor alignment control. The storage stability of the composition for use can be improved.

  [B] The ester structure-containing compound is selected from the group consisting of an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid, and a t-butyl ester structure of carboxylic acid in the molecule. It is a compound having two or more of at least one kind of structure. [B] The ester structure-containing compound may be a compound having two or more of the same kind of structures among these structures, or a compound having two or more of the different kinds of structures among these structures. There may be. Examples of the group containing an acetal ester structure of the carboxylic acid include groups represented by the following formulas (B-1) and (B-2).

（式（Ｂ−１）中、Ｒ^１３及びＲ^１４は、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜１０の脂環式基、炭素数６〜１０のアリール基又は炭素数７〜１０のアラルキル基であり、
式（Ｂ−２）中、ｎ１は２〜１０の整数である。）

(In formula (B-1), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or An aralkyl group having 7 to 10 carbon atoms,
In formula (B-2), n1 is an integer of 2-10. )

Here, for R ¹³ in the above formula (B-1),
A methyl group as an alkyl group;
A cyclohexyl group as the alicyclic group;
A phenyl group as an aryl group;
A benzyl group is preferred as the aralkyl group,
An alkyl group having 1 to 6 carbon atoms as the alkyl group for R ¹⁴ ;
An alicyclic group having 6 to 10 carbon atoms as the alicyclic group;
A phenyl group as an aryl group;
As the aralkyl group, a benzyl group or 2-phenylethyl group is preferable. N1 in Formula (B-2) is preferably 3 or 4.

Examples of the group represented by the formula (B-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-i-propoxyethoxycarbonyl group, 1 -N-butoxyethoxycarbonyl group, 1-i-butoxyethoxycarbonyl group, 1-sec-butoxyethoxycarbonyl group, 1-t-butoxyethoxycarbonyl group, 1-cyclopentyloxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group 1-norbornyloxyethoxycarbonyl group, 1-bornyloxyethoxycarbonyl group, 1-phenoxyethoxycarbonyl group, 1- (1-naphthyloxy) ethoxycarbonyl group, 1-benzyloxyethoxycarbonyl group, 1-phenethylo Ciethoxycarbonyl group, (cyclohexyl) (methoxy) methoxycarbonyl group, (cyclohexyl) (ethoxy) methoxycarbonyl group, (cyclohexyl) (n-propoxy) methoxycarbonyl group, (cyclohexyl) (i-propoxy) methoxycarbonyl group, (Cyclohexyl) (cyclohexyloxy) methoxycarbonyl group, (cyclohexyl) (phenoxy) methoxycarbonyl group, (cyclohexyl) (benzyloxy) methoxycarbonyl group, (phenyl) (methoxy) methoxycarbonyl group, (phenyl) (ethoxy) methoxycarbonyl group , (Phenyl) (n-propoxy) methoxycarbonyl group, (phenyl) (i-propoxy) methoxycarbonyl group, (phenyl) (cyclohexyloxy) methoxycarbonyl Nyl group, (phenyl) (phenoxy) methoxycarbonyl group, (phenyl) (benzyloxy) methoxycarbonyl group, (benzyl) (methoxy) methoxycarbonyl group, (benzyl) (ethoxy) methoxycarbonyl group, (benzyl) (n- (Propoxy) methoxycarbonyl group, (benzyl) (i-propoxy) methoxycarbonyl group, (benzyl) (cyclohexyloxy) methoxycarbonyl group, (benzyl) (phenoxy) methoxycarbonyl group, (benzyl) (benzyloxy) methoxycarbonyl group, etc. ;
Examples of the group represented by the formula (B-2) include a 2-tetrahydrofuranyloxycarbonyl group, a 2-tetrahydropyranyloxycarbonyl group, and the like.

  Of these, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group and the like are preferable.

  As group containing the ketal ester structure of the said carboxylic acid, group represented by each of following formula (B-3)-(B-5) can be mentioned, for example.

（式（Ｂ−３）中、Ｒ^１５は炭素数１〜１２のアルキル基であり、Ｒ^１６及びＲ^１７は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数３〜２０の脂環式基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基である。
式（Ｂ−４）中、Ｒ^１８は炭素数１〜１２のアルキル基であり、ｎ２は２〜８の整数である。
式（Ｂ−５）中、Ｒ^１９は炭素数１〜１２のアルキル基であり、ｎ３は２〜８の整数である。）

(In the formula (B-3), R ¹⁵ is an alkyl group having 1 to 12 carbon atoms, and R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 12 carbon atoms and 3 to 20 carbon atoms. An alicyclic group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
In the formula (B-4), R ¹⁸ is an alkyl group having 1 to 12 carbon atoms, and n2 is an integer of 2 to 8.
In the formula (B-5), R ¹⁹ is an alkyl group having 1 to 12 carbon atoms, and n3 is an integer of 2 to 8. )

Here, the alkyl group of R ¹⁵ in the above formula (B-3) is preferably a methyl group,
For R ^{16 a} methyl group as an alkyl group;
A cyclohexyl group as the alicyclic group;
A phenyl group as an aryl group;
A benzyl group is preferred as the aralkyl group,
For R ¹⁷ , an alkyl group having 1 to 6 carbon atoms as an alkyl group;
An alicyclic group having 6 to 10 carbon atoms as the alicyclic group;
A phenyl group as an aryl group;
A benzyl group or 2-phenylethyl group is preferred as the aralkyl group,
In the formula (B-4), a methyl group as the alkyl group of R ¹⁸ and n2 is preferably 3 or 4, respectively.
In the formula (B-5), the alkyl group for R ¹⁹ is preferably a methyl group, and n3 is preferably 3 or 4.

  Examples of the group represented by the formula (B-3) include 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-ethoxyethoxycarbonyl group, 1-methyl-1-n-propoxyethoxycarbonyl. Group, 1-methyl-1-i-propoxyethoxycarbonyl group, 1-methyl-1-n-butoxyethoxycarbonyl group, 1-methyl-1-i-butoxyethoxycarbonyl group, 1-methyl-1-sec-butoxy Ethoxycarbonyl group, 1-methyl-1-t-butoxyethoxycarbonyl group, 1-methyl-1-cyclopentyloxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group, 1-methyl-1-norbornyl Oxyethoxycarbonyl group, 1-methyl-1-bornyloxyethoxycarbonyl 1-methyl-1-phenoxyethoxycarbonyl group, 1-methyl-1- (1-naphthyloxy) ethoxycarbonyl group, 1-methyl-1-benzyloxyethoxycarbonyl group, 1-methyl-1-phenethyloxyethoxycarbonyl Group, 1-cyclohexyl-1-methoxyethoxycarbonyl group, 1-cyclohexyl-1-ethoxyethoxycarbonyl group, 1-cyclohexyl-1-n-propoxyethoxycarbonyl group, 1-cyclohexyl-1-i-propoxyethoxycarbonyl group, 1-cyclohexyl-1-cyclohexyloxyethoxycarbonyl group, 1-cyclohexyl-1-phenoxyethoxycarbonyl group, 1-cyclohexyl-1-benzyloxyethoxycarbonyl group, 1-phenyl-1-methoxyethoxycarbonyl Nyl group, 1-phenyl-1-ethoxyethoxycarbonyl group, 1-phenyl-1-n-propoxyethoxycarbonyl group, 1-phenyl-1-i-propoxyethoxycarbonyl group, 1-phenyl-1-cyclohexyloxyethoxycarbonyl Group, 1-phenyl-1-phenoxyethoxycarbonyl group, 1-phenyl-1-benzyloxyethoxycarbonyl group, 1-benzyl-1-methoxyethoxycarbonyl group, 1-benzyl-1-ethoxyethoxycarbonyl group, 1-benzyl -1-n-propoxyethoxycarbonyl group, 1-benzyl-1-i-propoxyethoxycarbonyl group, 1-benzyl-1-cyclohexyloxyethoxycarbonyl group, 1-benzyl-1-phenoxyethoxycarbonyl group, 1-benzyl- 1-Benz A ruoxyethoxycarbonyl group, etc .;

Examples of the group represented by the formula (B-4) include a 2- (2-methyltetrahydrofuranyl) oxycarbonyl group, a 2- (2-methyltetrahydropyranyl) oxycarbonyl group, and the like;
Examples of the group represented by the above formula (B-5) include 1-methoxycyclopentyloxycarbonyl group, 1-methoxycyclohexyloxycarbonyl group, and the like.

  Of these, 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-cyclohexyloxyethoxycarbonyl group and the like are preferable.

  Examples of the group containing a 1-alkylcycloalkyl ester structure of the carboxylic acid include a group represented by the following formula (B-6).

（式（Ｂ−６）中、Ｒ^２０は炭素数１〜１２のアルキル基であり、ｎ４は１〜８の整数である。）

(In Formula (B-6), R ²⁰ is an alkyl group having 1 to 12 carbon atoms, and n4 is an integer of 1 to 8.)

The alkyl group for R ^{20 in} the above formula (B-6) is preferably an alkyl group having 1 to 10 carbon atoms.

  Examples of the group represented by the formula (B-6) include 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentoxycarbonyl group, 1-methylcyclohexyloxycarbonyl group, 1-methylcycloheptyloxycarbonyl group, 1-methylcyclooctyloxycarbonyl group, 1-methylcyclononyloxycarbonyl group, 1-methylcyclodecyloxycarbonyl group, 1-ethylcyclopropoxycarbonyl group, 1-ethylcyclobutoxy Carbonyl group, 1-ethylcyclopentoxycarbonyl group, 1-ethylcyclohexyloxycarbonyl group, 1-ethylcycloheptyloxycarbonyl group, 1-ethylcyclooctyloxycarbonyl group, 1-ethylcyclononoxycarbonyl group, Ethyl shik Decyloxycarbonyl group, 1- (iso) propylcyclopropoxycarbonyl group, 1- (iso) propylcyclobutoxycarbonyl group, 1- (iso) propylcyclopentoxycarbonyl group, 1- (iso) propylcyclohexyloxycarbonyl group, 1- (iso) propylcycloheptyloxycarbonyl group, 1- (iso) propylcyclooctyloxycarbonyl group, 1- (iso) propylcyclononyloxycarbonyl group, 1- (iso) propylcyclodecyloxycarbonyl group, 1 -(Iso) butylcyclopropoxycarbonyl group, 1- (iso) butylcyclobutoxycarbonyl group, 1- (iso) butylcyclopentoxycarbonyl group, 1- (iso) butylcyclohexyloxycarbonyl group, 1- (iso) butyl Cycloheptyloxycarboni 1- (iso) butylcyclooctyloxycarbonyl group, 1- (iso) butylcyclononyloxycarbonyl group, 1- (iso) butylcyclodecyloxycarbonyl group, 1- (iso) pentylcyclopropoxycarbonyl group, -(Iso) pentylcyclobutoxycarbonyl group, 1- (iso) pentylcyclopentoxycarbonyl group, 1- (iso) pentylcyclohexyloxycarbonyl group, 1- (iso) pentylcycloheptyloxycarbonyl group, 1- (iso ) Pentylcyclooctyloxycarbonyl group, 1- (iso) pentylcyclononyloxycarbonyl group, 1- (iso) pentylcyclodecyloxycarbonyl group,

  1- (iso) hexylcyclopropoxycarbonyl group, 1- (iso) hexylcyclobutoxycarbonyl group, 1- (iso) hexylcyclopentoxycarbonyl group, 1- (iso) hexylcyclohexyloxycarbonyl group, 1- (iso) Hexylcycloheptyloxycarbonyl group, 1- (iso) hexylcyclooctyloxycarbonyl group, 1- (iso) hexylcyclononyloxycarbonyl group, 1- (iso) hexylcyclodecyloxycarbonyl group, 1- (iso) heptyl Cyclopropoxycarbonyl group, 1- (iso) heptylcyclobutoxycarbonyl group, 1- (iso) heptylcyclopentoxycarbonyl group, 1- (iso) heptylcyclohexyloxycarbonyl group, 1- (iso) heptylcycloheptyloxycarbonyl The group 1- (iso Heptylcyclooctyloxycarbonyl group, 1- (iso) heptylcyclononyloxycarbonyl group, 1- (iso) heptylcyclodecyloxycarbonyl group, 1- (iso) octylcyclopropoxycarbonyl group, 1- (iso) octylcyclobutoxy Carbonyl group, 1- (iso) octylcyclopentoxycarbonyl group, 1- (iso) octylcyclohexyloxycarbonyl group, 1- (iso) octylcycloheptyloxycarbonyl group, 1- (iso) octylcyclooctyloxycarbonyl group 1- (iso) octylcyclononyloxycarbonyl group, 1- (iso) octylcyclodecyloxycarbonyl group, and the like.

  The group containing the t-butyl ester structure of the carboxylic acid is a t-butoxycarbonyl group.

As the [B] ester structure-containing compound in the present invention, a compound represented by the following formula (B) is preferable.
B _n R (B)
(In the formula (B), B is a group represented by any one of the above formulas (B-1) to (B-5) or a t-butoxycarbonyl group, n is 2, and R is a single bond. N is an integer of 2 to 10 and R is an n-valent group obtained by removing hydrogen from a heterocyclic compound having 3 to 10 carbon atoms or an n-valent hydrocarbon group having 1 to 18 carbon atoms .)
n is preferably 2 or 3.

  As specific examples of R in the above formula (B), when n is 2, a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a 1,2-phenylene group, a 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthalenyl group, 5-sodium sulfo-1,3-phenylene group, 5-tetrabutylphosphonium sulfo-1,3-phenylene group and the like;

  In the case where n is 3, the following formula

And a group represented by the formula: benzene-1,3,5-triyl group and the like. As said alkylene group, a linear thing is preferable.

  The [B] ester structure-containing compound represented by the above formula (B) can be synthesized by an organic chemistry standard method or by appropriately combining organic chemistry standard methods.

For example, a compound in which the group B in the formula (B) is a group represented by the formula (B-1) (except for the case where R ¹³ is a phenyl group) is preferably in the presence of a phosphoric acid catalyst. in compound R- _{(COOH) n} (wherein, R and n are each the same definition as in the formula (B).) and a compound ^{R 14 -O-CH = R 13} '( provided ^{that, R 14} is the formula (B-1) is synonymous, and R ¹³ _′ is a group obtained by removing a hydrogen atom from the 1-position carbon of the group R ¹³ in the above formula (B-1). Can be synthesized.

The compound in which the group B in the formula (B) is a group represented by the formula (B-2) is preferably a compound R- (COOH) _n (wherein R and R in the presence of a p-toluenesulfonic acid catalyst). n is synonymous with that in the above formula (B).) and a compound represented by the following formula can be added.

（式中、ｎ１は上記式（Ｂ−２）におけるのと同義である。）

(In the formula, n1 has the same meaning as in the above formula (B-2).)

  The content of the [B] ester structure-containing compound in the composition for controlling the alignment of organic EL light emitters is not particularly limited as long as it is determined in consideration of the required heat resistance and the like, but with respect to 100 parts by mass of the [A] compound [B] 0.1-50 parts by mass of the ester structure-containing compound is preferable, 1-20 parts by mass is more preferable, and 2-10 parts by mass is particularly preferable.

<Other polymers>
Said other polymer can be used in order to improve the solution characteristic of the composition for organic EL light emitting body orientation control of this invention, and the electrical property of the organic EL light emitting body orientation control film obtained more. Such other polymer is selected from the group consisting of, for example, a polyorganosiloxane having a repeating unit having a structure different from the repeating unit represented by the above formula (3), a hydrolyzate thereof, and a condensate of the hydrolyzate. At least one (hereinafter also referred to simply as “other polyorganosiloxane”), polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) An acrylate etc. can be mentioned.

<Other polyorganosiloxane>
As described above, the organic EL light emitter orientation control composition of the present invention may contain another polyorganosiloxane in addition to the [A] compound. When other polyorganosiloxane is contained in the present invention, at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (5), a hydrolyzate thereof, and a condensate of the hydrolyzate. Preferably it is a seed.

（式（５）中、Ｘ^２は水酸基、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数１〜６のアルコキシ基又は炭素数６〜２０のアリール基であり、Ｙ^２は水酸基又は炭素数１〜１０のアルコキシ基である。）

(In Formula (5), X ² is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and Y ² is a hydroxyl group or carbon. (It is an alkoxy group of formula 1 to 10.)

  When the composition for controlling alignment of organic EL light emitters contains the other polyorganosiloxane, most of the other polyorganosiloxane is present independently from the compound [A], Some may exist as a condensate with the [A] compound.

  Such other polyorganosiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter also referred to as “raw silane compound”), preferably an appropriate organic solvent. It can be synthesized by hydrolysis or hydrolysis / condensation in the presence of water and a catalyst.

  Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-. Butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-i-propoxysilane, ethyl Tri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi Chlorosilane; trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane and the like. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane are preferred.

  Examples of organic solvents that can optionally be used in the synthesis of other polyorganosiloxanes include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These can be used alone or in combination of two or more.

Examples of the alcohol compound include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol , Phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, monoalcohol compounds such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, the partial ethers of polyhydric alcohol compound and dipropylene glycol monopropyl ether, can be mentioned, respectively. These alcohol compounds may be used alone or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and di-i-. Monoketone compounds such as butyl ketone, methyl-n-hexyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, fenchon, acetophenone;
Acetylacetone, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 5-methyl-2,4-hexanedione, 2,4-octanedione, 3, 5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- Β-diketone compounds such as 2,4-heptanedione;
Examples thereof include γ-diketone compounds such as acetonylacetone. These ketone compounds may be used alone or in combination of two or more.

  Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide compounds may be used alone or in combination of two or more.

  Examples of the ester compound include ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, and i-butyl acetate. , Sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate Mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate , Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl malonate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid Examples thereof include n-amyl, dimethyl phthalate, and diethyl phthalate. These ester compounds may be used alone or in combination of two or more.

Examples of the other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholine, N-methylpyrrole, N— Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, 1 , 3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, and the like.
Of these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, or ester compounds are particularly preferred.

  The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.01 to 100 mol, more preferably 0, relative to 1 mol of the total amount of alkoxy groups and halogen atoms of the starting silane compound. 0.1 to 30 mol, and preferably 1 to 1.5 mol.

  Examples of catalysts that can be used in the synthesis of other polyorganosiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.

  Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bi (Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n- Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium,

  Triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) Titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl aceto) Acetate) titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t- Butoxy bis (ethylacetate Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris Titanium chelate compounds such as (ethyl acetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

  Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri -n- butoxy mono (ethylacetoacetate) zirconium, tri -sec- butoxy mono (ethylacetoacetate) zirconium, tri -t- butoxy mono (ethylacetoacetate) zirconium,

Diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) Zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl) Acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris Ethyl acetoacetate) zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis ( Zirconium chelate compounds such as ethyl acetoacetate) zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium;
Examples thereof include aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum.

  Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, adipic acid, methylmalonic acid, sebacic acid, gallic acid , Butyric acid, merit acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

  Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. These catalysts may be used alone or in combination of two or more.

  Of these catalysts, metal chelate compounds, organic acids or inorganic acids are preferred. As the metal chelate compound, a titanium chelate compound is particularly preferable.

  The amount of the catalyst to be used is preferably 0.001 to 10 parts by mass, more preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the raw material silane compound.

  The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.

  Water added in the synthesis of another polyorganosiloxane can be added intermittently or continuously in the raw material silane compound or in a solution obtained by dissolving the silane compound in an organic solvent.

  The reaction temperature in the synthesis of other polyorganosiloxane is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

<Use ratio of other polymer>
When the composition for controlling the alignment of organic EL light emitters of the present invention contains another polymer together with the [A] compound, the content of the other polymer is based on 100 parts by mass of the [A] compound. It is preferably 10,000 parts by mass or less. The more preferable content of the other polymer varies depending on the type of the other polymer.

  On the other hand, when the composition for controlling the alignment of organic EL light emitters of the present invention contains the [A] compound and other polyorganosiloxane, the preferred use ratio of both is other than 100 parts by mass of the [A] compound. The amount of the polyorganosiloxane is 100 to 2,000 parts by mass. When the composition for controlling the alignment of organic EL light emitters of the present invention contains another polymer together with the compound [A], the other polymer is preferably another polyorganosiloxane. .

<Curing agent, curing catalyst, and curing accelerator>
The said hardening | curing agent and hardening catalyst can be contained in the composition for organic EL light-emitting body orientation control of this invention for the purpose of making the crosslinking reaction of a [A] compound stronger. The said hardening accelerator can be contained in the composition for organic EL light-emitting body orientation control of this invention in order to accelerate | stimulate the hardening reaction which a hardening | curing agent controls.

  As said hardening | curing agent, the hardening | curing agent generally used for hardening of the curable compound containing the curable compound which has an epoxy group, or the compound which has an epoxy group can be used. Examples of such curing agents include polyvalent amines, polyvalent carboxylic acid anhydrides, and polyvalent carboxylic acids.

  Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides.

  Specific examples of the cyclohexanetricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane- 1,2,3-tricarboxylic acid-2,3-acid anhydride, and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic acid anhydride, methylnadic acid anhydride, Dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, the following formula (6)

（式（６）中、ｐは１〜２０の整数である。）
で表される化合物、及びポリアミック酸の合成に一般に用いられるテトラカルボン酸二無水物のほか、α−テルピネン、アロオシメン等の共役二重結合を有する脂環式化合物と無水マレイン酸とのディールス・アルダー反応生成物及びこれらの水素添加物等を挙げることができる。

(In Formula (6), p is an integer of 1-20.)
In addition to tetracarboxylic dianhydrides generally used for the synthesis of polyamic acids, Diels-Alder of alicyclic compounds having conjugated double bonds such as α-terpinene and alloocimene and maleic anhydride Reaction products and their hydrogenated products can be mentioned.

  As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, aluminum trisacetylacetonate, or the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.

Examples of the curing accelerator include imidazole compounds;
Quaternary phosphorus compounds;
Quaternary amine compounds;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as dicyandiamide, amine addition type accelerators such as adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator whose surface is covered with a polymer such as a quaternary phosphonium salt;
An amine salt type latent curing accelerator;
Examples thereof include high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

<Epoxy compound>
The above epoxy compound may be included in the composition for controlling the alignment of organic EL light emitters of the present invention from the viewpoint of improving the adhesion of the formed organic EL light emitter alignment control film to the substrate or the anode electrode surface.

  Examples of such epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′— Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4 ′ Diaminodiphenylmethane, N, N, - diglycidyl - benzylamine, N, N-diglycidyl - may be mentioned as being preferred amino methyl cyclohexane.

  When the composition for organic EL light emitter alignment control of the present invention contains an epoxy compound, the content ratio is 100 parts by mass in total of the above-mentioned [A] compound and other polymer optionally used. The amount is preferably 0.01 to 40 parts by mass, and more preferably 0.1 to 30 parts by mass.

  In addition, when the composition for organic EL light emitter alignment control of the present invention contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing the crosslinking reaction. .

<Functional silane compound>
The said functional silane compound can be used in order to improve the adhesiveness with the anode electrode of the organic electroluminescent light emitting body orientation control film obtained. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane In addition, JP-A 63-2 It described in 1922 JP, a reaction product of the silane compound having a tetracarboxylic dianhydride and an amino group.

  When the composition for organic EL light emitter alignment control of the present invention contains a functional silane compound, the content ratio is 100 parts by mass in total of the [A] compound and another polymer optionally used. On the other hand, it is preferably 50 parts by mass or less, more preferably 20 parts by mass or less.

<Surfactant>
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. it can.

  When the composition for controlling the alignment of organic EL light emitters contains the surfactant, the content is preferably 10 parts by weight or less with respect to 100 parts by weight as a whole of the composition for controlling alignment of organic EL light emitters. Yes, more preferably 1 part by mass or less.

<Photosensitizing compound>
The photosensitizing compound that can be contained in the composition for controlling the alignment of organic EL light emitters is a carboxyl group, a hydroxyl group, —SH, —NCO, —NHR (where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). A compound having at least one group selected from the group consisting of —CH═CH ₂ and SO ₂ Cl and a photosensitizing structure. By reacting the polyorganosiloxane having the epoxy group with a mixture of a specific cinnamic acid derivative and a photosensitizing compound, the [A] compound contained in the composition for controlling the alignment of an organic EL phosphor of the present invention is: The photosensitive structure derived from the specific cinnamic acid derivative (cinnamic acid structure) and the photosensitized structure derived from the photosensitizing compound are combined. This photosensitizing structure has a function of being excited by light irradiation and giving this excitation energy to the adjacent photosensitive structure in the polymer. This excited state may be a singlet or a triplet, but is preferably a triplet in view of long life and efficient energy transfer. The light absorbed by the photosensitizing structure is preferably ultraviolet rays or visible rays having a wavelength in the range of 150 to 600 nm. Light with a wavelength shorter than the above lower limit cannot be used in a photo-alignment method because it cannot be handled by a normal optical system. On the other hand, light having a wavelength longer than the above upper limit has a small energy and hardly induces an excited state of the photosensitizing structure.

  Examples of such photosensitizing structures include acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure, fluorene structure, naphthalene structure, anthracene structure, acridine structure, indole structure, etc. Or in combination of two or more. These photosensitizing structures are groups obtained by removing 1 to 4 hydrogen atoms from acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene, acridine or indole, respectively. A structure consisting of Here, each of the acetophenone structure, the carbazole structure, and the indole structure is preferably a structure composed of groups obtained by removing 1 to 4 hydrogen atoms of the benzene ring of acetophenone, carbazole, or indole. Among these photosensitizing structures, it is preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure. Particularly preferred is at least one selected from the group consisting of a structure and a nitroaryl structure.

  The photosensitizing compound is preferably a compound having a carboxyl group and a photosensitizing structure, and more preferable compounds include, for example, compounds represented by the following formulas (H-1) to (H-10): Can be mentioned.

（式中、ｑは１〜６の整数である。）

(Wherein q is an integer of 1 to 6)

  The compound [A] used in the present invention is preferably an organic solvent, preferably in the presence of a catalyst, in addition to the polyorganosiloxane having an epoxy group as described above and a specific cinnamic acid derivative, and a photosensitizing compound. You may synthesize | combine by making it react in. In this case, the specific cinnamic acid derivative is preferably 0.001 to 1 mol, more preferably 0.1 to 1 mol, still more preferably 0.2 to 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group. Used in the range of ~ 0.9 mol. The photosensitizing compound is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, still more preferably 0.001 mol per mol of silicon atom of the polyorganosiloxane having an epoxy group. It is used in the range of 001 to 0.1 mol.

<Preparation of composition for controlling orientation of organic EL phosphor>
As described above, the composition for controlling the alignment of organic EL light emitters of the present invention contains the [A] compound as an essential component and, in addition, other components as necessary, preferably each component. Is prepared as a solution-like composition dissolved in an organic solvent. The photo-alignment compound and other components (for example, at least one polymer selected from the group consisting of polyamic acid and polyimide, other polyorganosiloxanes, etc.) are organic EL phosphor alignment control compositions. In any state of the alignment layer and the organic EL light emitter alignment control film, they may be partially bonded to each other.

  As the organic solvent that can be used for preparing the composition for controlling the alignment of the organic EL phosphor of the present invention, those that dissolve the [A] compound and other components used and do not react with these are preferable. . The organic solvent that can be preferably used in the composition for controlling the alignment of the organic EL phosphor of the present invention varies depending on the type of other polymer that is optionally added.

  In the composition for controlling the alignment of the organic EL phosphor of the present invention, examples of the preferable organic solvent for the compound [A] include the organic solvents exemplified above as those used for the synthesis of polyamic acid. At this time, you may use together the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention. These organic solvents can be used alone or in combination of two or more.

  On the other hand, as a preferable organic solvent in the case where the composition for controlling the alignment of organic EL light emitters of the present invention contains the [A] compound and other polyorganosiloxane as a polymer, for example, 1-ethoxy-2-propanol, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl Sorb), ethylene glycol monoamyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-acetate -Propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, acetic acid 2 -Ethylhexyl, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

  A preferable solvent used for the preparation of the composition for controlling the alignment of the organic EL phosphor of the present invention is obtained by combining one or more of the above-mentioned organic solvents according to whether or not other polymers are used and their types. Can do. In such a solvent, each component contained in the composition for controlling orientation of organic EL light emitter does not precipitate at the following preferable solid content concentration, and the surface tension of the composition for controlling orientation of organic EL light emitter is 25 to 40 mN. / M.

  The solid content concentration of the organic EL light emitter alignment control composition, that is, the ratio of the mass of all components other than the solvent in the organic EL light emitter alignment control composition to the total mass of the organic EL light emitter alignment control composition Is selected in consideration of viscosity, volatility and the like, but is preferably in the range of 1 to 10% by mass. The composition for controlling the orientation of organic EL light emitters of the present invention is applied on a substrate or an anode electrode to form a coating film that becomes an orientation control film for organic EL light emitters, but the solid content concentration is 1% by mass or more. In this case, the film thickness of the coating film is less likely to be too small, and a good organic EL light emitter alignment control film can be obtained. On the other hand, when the solid content concentration is 10% by mass or less, it is possible to obtain an excellent organic EL light emitter alignment control film by suppressing the film thickness of the coating film from becoming excessive, and to obtain an organic EL light emitter. It is possible to prevent the viscosity of the composition for orientation control from increasing and to improve the coating characteristics. The particularly preferable range of the solid content concentration varies depending on the method employed when applying the composition for controlling the orientation of the organic EL light emitter to the substrate or the anode electrode. For example, when the spinner method is used, the range of 1.5 to 4.5% by mass is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by mass, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.

  The temperature at the time of preparing the composition for controlling the alignment of the organic EL phosphor of the present invention is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

<Organic EL emitter alignment control film>
The composition for controlling the alignment of the organic EL phosphor of the present invention can be suitably used for forming an alignment control film that imparts anisotropy to the organic EL phosphor layer by a photo-alignment method.

  As a method of forming the organic EL light emitter alignment control film, for example, an anode electrode is formed on a substrate, a coating film is formed by the organic EL light emitter alignment control composition so as to cover the anode electrode, and then A method of imparting organic EL light emitter alignment ability by a photo-alignment method in which the coating film is irradiated with anisotropic polarized light or the like can be mentioned.

  First, the organic EL light emitter orientation control composition of the present invention is applied by an appropriate application method such as a roll coater method, a spinner method, a printing method, or an ink jet method. Then, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

  Next, the organic EL light emitter alignment ability is imparted by irradiating the coating film with linearly polarized light, partially polarized light or non-polarized light. Here, as the light, for example, ultraviolet light and visible light including light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 nm to 400 nm is preferable. When the light to be used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized light, the direction of irradiation needs to be an oblique direction.

  As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.

Although it does not specifically limit as an irradiation amount of light, Preferably it is 1 J / m < ² > or more and less than 10,000 J / m < ² >, More preferably, it is 10-3,000 J / m < ² >. In addition, when providing organic EL light-emitting body orientation ability with the photo-alignment method with respect to the coating film formed from the conventionally known composition for organic EL light-emitting body orientation control, light irradiation of 10,000 J / m < ² > or more The amount was necessary. However, when the composition for controlling the alignment of the organic EL phosphor of the present invention is used, good organic properties can be obtained even when the radiation dose during the photo-alignment method is 3,000 J / m ² or less, and even 1,000 J / m ² or less. EL light emitter alignment ability can be imparted, which contributes to improvement of productivity of organic EL elements and reduction of manufacturing costs.

  When applying the organic EL phosphor alignment control composition, a functional silane compound, titanate, or the like is applied in advance on the substrate or anode electrode in order to further improve the adhesion to the substrate or anode electrode. You may keep it.

<Organic EL element and manufacturing method thereof>
The organic EL element of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the organic EL element of the present invention. The organic EL element 1 is formed on the anode electrode 3 formed on the substrate 2, the organic EL light emitter alignment control film 4 formed so as to cover the anode electrode 3, and the organic EL light emitter alignment control film 4. The organic EL light emitting layer 5 and the cathode electrode 6 formed on the organic EL light emitting layer 5 are provided.

Moreover, the manufacturing method of the organic EL element of this invention is the process of forming a coating film using the said composition for organic EL light emitter orientation control so that the anode electrode formed on the board | substrate may be covered, A step of forming an organic EL light emitter alignment control film by irradiating linearly polarized light, a step of forming an organic EL light emitter layer on the organic EL light emitter alignment control film, and a cathode electrode on the organic EL light emitter layer Forming. Hereinafter, each element will be described.

<Board>
The substrate 2 has a high light transmittance in the visible light region and does not change in the process of forming the organic EL element. The substrate 2 may be a rigid plate or a flexible plate, such as a glass plate, a plastic plate, A molecular film, a silicon plate, and a laminated plate obtained by laminating these are preferably used.

  As the resin constituting the plastic plate or the polymer film, for example, a resin that does not dissolve in the coating liquid used when the organic EL light-emitting layer 5 and a hole injection layer described later are formed by a coating method is preferable. Specifically, low density or high density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-norbornene copolymer, ethylene- Polyolefin resins such as domon copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; nylon-6 , Nylon-6,6, metaxylenediamine-adipic acid condensation polymer; amide resin such as polymethylmethacrylamide; acrylic resin such as polymethylmethacrylate; polystyrene, styrene-acrylonitrile copolymer, styrene Styrene-acrylonitrile resins such as acrylonitrile-butadiene copolymer and polyacrylonitrile; Hydrophobized cellulose resins such as cellulose triacetate and cellulose diacetate; Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, etc. Halogen-containing resin; hydrogen bonding resin such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivative; polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenylene oxide resin, polymethylene oxide resin And engineering plastic resins such as polyarylate resin and liquid crystal resin.

  Since the substrate is required to have heat resistance in the production process, among the above resins, a glass transition point Tg of 150 ° C. or higher is preferable, 180 ° C. or higher is more preferable, and 200 ° C. or higher is more preferable. .

  Note that the top emission type organic EL element does not need to be a transparent substrate because light is not extracted from the substrate, and may be a light-transmitting substrate or a light-impermeable substrate.

<Anode electrode>
The anode electrode 3 is realized by a thin film having translucency and conductivity, and is configured by, for example, a metal oxide film, a metal thin film, or the like. Specifically, thin films of indium oxide, zinc oxide, tin oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, and the like A thin film of ITO, IZO, tin oxide or the like is preferable. As the anode electrode 3, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. The thickness of the anode electrode 3 can be appropriately set in consideration of light transmittance and conductivity, and is generally about 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. . When light is not extracted from the anode electrode side, the anode electrode may be formed of an opaque anode.

  Examples of the method for forming the anode electrode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

<Organic EL emitter alignment control film>
As the organic EL light emitter alignment control film 4 constituting the organic EL element 1, the organic EL light emitter alignment control film of the present invention described above is used. Since the configuration and the manufacturing method of the organic EL light emitter alignment control film 4 are as described above, they are omitted here.

<Organic EL phosphor layer>
The organic EL light-emitting layer 5 includes a light-emitting organic compound that is an organic EL light-emitting body, and the organic compound that emits light (hereinafter also simply referred to as “light-emitting material”) is an organic substance that emits fluorescence and / or phosphorescence. Or this organic substance and a dopant are comprised. The dopant is added for the purpose of, for example, improving the light emission efficiency or changing the light emission wavelength. The light emitting material may be either a low molecular compound or a high molecular compound, and a material exhibiting liquid crystallinity is preferable. Examples of the light emitting material constituting the organic EL light emitting layer include the following. The organic EL phosphor layer preferably emits white light.

  Examples of dye-based light-emitting materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, and thiophene rings. Examples thereof include compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

  As a metal complex-based light-emitting material, a central metal has Al, Zn, Be or the like, or a rare earth metal such as Tb, Eu, or Dy, and a ligand has oxadiazole, thiadiazole, phenylpyridine, or phenylbenzo. Examples include metal complexes having imidazole and quinoline structures, such as iridium complexes, platinum complexes and other metal complexes having light emission from triplet excited states, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc. A complex, a benzothiazole zinc complex, an azomethylzinc complex, a porphyrin zinc complex, a europium complex, etc. can be mentioned.

  Examples of the polymer-based light-emitting material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, and polyvinylcarbazole derivatives, and the above-described dye-based light-emitting materials and metals. Examples include those obtained by polymerizing complex light emitting materials.

  Among the above light emitting materials, materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.

  Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.

  Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyfluorene derivatives, and the like. Among these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, polyfluorene derivatives and the like are preferable.

  Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like.

  Specific examples of the light-emitting material exhibiting liquid crystallinity include, for example, Macromolecules 2003, 36, 3457-3464, Appl. Phys. Lett. 2006, 89, 121920, J. MoI. Phys. Chem. B107, 4887 (2003), Chemical Society of Japan Spring Annual Meeting 3G7-40, Proc. Examples thereof include liquid crystal luminescent materials described in SPIE 2005, 5963, and 59360C.

  Of these light emitting materials, those having liquid crystallinity in a region from room temperature to 50 degrees are preferable from the viewpoint of easily aligning materials. In addition, the thickness of such an organic EL light emitting layer is usually about 2 nm to 2000 nm.

  In the step of forming the organic EL light emitting layer, first, a film for an organic EL light emitting layer is formed by a coating method using a coating liquid containing a liquid crystalline compound (light emitting material) that becomes the organic EL light emitting layer, for example.

  The coating solution for the organic EL phosphor layer may be a solution or an emulsion. The solvent of the coating liquid for the organic EL phosphor layer may be any liquid that dissolves the liquid crystal compound (light emitting material). For example, the solvents mentioned as the solvent for the coating liquid for the hole injection layer can be appropriately used. The dispersion medium may be any liquid that can uniformly disperse the liquid crystalline compound (light emitting material).

  Examples of the coating method include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spray coating. And a coating method such as a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an inkjet printing method. A coating method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method, and an ink jet printing method is preferable in that pattern formation and multicolor coating are easy. In the case of a sublimable low molecular compound, a vacuum deposition method can be used. Furthermore, the organic EL light emitting layer can be formed only at a desired place by a method such as laser transfer or thermal transfer.

  Since the organic EL luminous body layer thus formed is formed on the organic EL luminous body alignment control film, the organic EL luminous body is highly uniaxially oriented and exhibits excellent polarized light emission efficiency, Even after the heat load, the initial luminous efficiency can be maintained at a high rate.

<Cathode electrode>
The cathode electrode 6 functions as a cathode. As such a material of the cathode electrode 6, a material having a small work function and easy electron injection into the organic EL light emitting layer 5 is preferable, and a material having high electric conductivity is preferable. Specifically, metals such as alkali metals, alkaline earth metals, transition metals, and group III-B metals can be used. More specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium A metal such as strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, two or more alloys of the above metals, or one or more of them, An alloy with one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, a graphite intercalation compound, or the like is used. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, calcium-aluminum alloys, and the like. .

  When the cathode electrode is constituted by a transparent electrode, the cathode electrode is constituted by a laminated body in which, for example, a thin film made of the above-described material and a thin film made of a conductive metal oxide or a conductive organic material are laminated. .

  In the organic EL element, in addition to the above configuration, a hole injection layer may be provided between the anode electrode and the organic EL light emitter alignment control film as necessary in order to improve the hole injection efficiency.

<Hole injection layer>
Examples of the hole injection material include phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, polythiophene derivatives, and the like.

  In the step of forming the hole injection layer, first, a functional layer thin film (hole injection layer film) is formed by a coating method using a coating liquid containing a hole injection material having a hole injection function, for example.

  The coating solution for the hole injection layer may be a solution or an emulsion. The solvent of the coating solution for the hole injection layer may be a liquid that dissolves the hole injection material, and the dispersion medium may be a liquid that can uniformly disperse the hole injection material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, and butyl acetate. And ester solvents such as ethyl cellosolve acetate and water.

  As the coating method, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, An offset printing method, an inkjet printing method, etc. can be mentioned.

  In the organic EL element 1 of FIG. 1, an organic EL light emitter orientation control film 4 and an organic EL light emitter layer 5 are disposed between an anode electrode 2 and a cathode electrode 6, and the anode electrode 2 and the organic EL element are arranged as necessary. A hole injection layer is disposed between the phosphor alignment control film 4. However, the configuration of the organic EL element 1 is not limited to the configuration shown in FIG. Hereinafter, an example of an element configuration between the anode electrode and the cathode electrode of the organic EL element will be described. The anode electrode and the cathode electrode may be at least transparent as long as the electrode arranged on the light extraction side is used, and one of them may be used as an anode and the other as a cathode. An example of the element configuration will be described without specifying the polarity of the anode electrode and the cathode electrode, with either one being the anode electrode and the other being the cathode electrode.

  As described above, it is sufficient that at least one organic EL light emitting layer is provided between the anode and the cathode, and a plurality of organic EL light emitting layers and / or organic ELs are provided between the anode and the cathode. One or a plurality of layers different from the light emitting layer may be provided.

  Examples of the layer provided between the cathode and the organic EL light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer. When both the electron injection layer and the electron transport layer are provided between the cathode and the organic EL phosphor layer, the layer located on the side close to the cathode is called the electron injection layer, and the organic EL phosphor layer The layer located on the near side is called an electron transport layer.

  The electron injection layer is a layer having a function of improving electron injection efficiency from the cathode. The electron transport layer is a layer having a function of improving electron injection from the cathode, the electron injection layer, or the electron transport layer closer to the cathode. The hole blocking layer is a layer having a function of blocking hole transport. In some cases, the electron injection layer or the electron transport layer also serves as a hole blocking layer.

  Examples of the layer provided between the anode and the organic EL light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer. When both the hole injection layer and the hole transport layer are provided between the anode and the organic EL phosphor layer, the layer located on the side close to the anode is referred to as a hole injection layer, and the organic EL phosphor layer A layer located on the side closer to the hole is called a hole transport layer.

  The hole injection layer is a layer having a function of improving hole injection efficiency from the anode. The hole transport layer is a layer having a function of improving hole injection from the anode, the hole injection layer, or the hole transport layer closer to the anode. The electron blocking layer is a layer having a function of blocking electron transport. The hole injection layer or the hole transport layer may also serve as the electron blocking layer.

  The electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer.

A specific example of the layer structure that the organic EL element can take is shown below.
a) Anode / hole transport layer / organic EL phosphor layer / cathode b) Anode / organic EL phosphor layer / electron transport layer / cathode c) Anode / hole transport layer / organic EL phosphor layer / electron transport layer / Cathode d) Anode / charge injection layer / organic EL emitter layer / cathode e) Anode / organic EL emitter layer / charge injection layer / cathode f) Anode / charge injection layer / organic EL emitter layer / charge injection layer / cathode g) Anode / charge injection layer / hole transport layer / organic EL phosphor layer / cathode h) Anode / hole transport layer / organic EL phosphor layer / charge injection layer / cathode i) Anode / charge injection layer / hole Transport layer / organic EL phosphor layer / charge injection layer / cathode j) anode / charge injection layer / organic EL phosphor layer / charge transport layer / cathode k) anode / organic EL phosphor layer / electron transport layer / charge injection layer / Cathode l) Anode / charge injection layer / organic EL phosphor layer / electron transport layer / charge injection layer / cathode m) anode / Load injection layer / hole transport layer / organic EL phosphor layer / charge transport layer / cathode n) Anode / hole transport layer / organic EL phosphor layer / electron transport layer / charge injection layer / cathode o) Anode / charge injection Layer / hole transport layer / organic EL light emitting layer / electron transport layer / charge injection layer / cathode (here, the symbol “/” indicates that two layers sandwiching the symbol “/” are adjacently stacked) The same shall apply hereinafter.)

In addition, the organic EL element may have two or more organic EL light emitting layers. As a specific example of an organic EL element having two organic EL phosphor layers,
p) Anode / charge injection layer / hole transport layer / organic EL emitter layer / electron transport layer / charge injection layer / electrode / charge injection layer / hole transport layer / organic EL emitter layer / electron transport layer / charge injection One having a layer structure of layer / cathode.

In addition, as an organic EL device having three or more organic EL light-emitting layers, (electrode / charge injection layer / hole transport layer / organic EL light-emitting layer / electron transport layer / charge injection layer) is one repeating unit. Then,
q) Including two or more repeating units such as anode / charge injection layer / hole transport layer / organic EL phosphor layer / electron transport layer / charge injection layer / repeating unit / repeating unit /. The thing which has a layer structure is mentioned.

  In the layer structures p and q, each layer other than the anode, the cathode, and the organic EL light emitting layer can be deleted as necessary.

  In the bottom emission type organic EL element that extracts light from the substrate 2, all the layers disposed on the substrate 2 side are formed of a transparent layer on the basis of the organic EL light emitting layer. As will be described later, in a so-called top emission type organic EL element that takes out light from the side opposite to the substrate with respect to the organic EL light emitting layer, it is disposed on the side opposite to the substrate with respect to the organic EL light emitting layer. All the layers to be formed are composed of transparent layers.

  The organic EL element may be further provided with an insulating layer having a film thickness of 2 nm or less adjacent to the electrode in order to improve the adhesion with the electrode or improve the charge injection from the electrode. In order to improve or prevent mixing, a thin buffer layer may be inserted at the interface between the adjacent layers.

  Hereinafter, a specific configuration of each layer will be described. Since the organic EL light-emitting layer 5 and the hole injection layer have been described above, redundant description will be omitted. Moreover, since the above-mentioned anode electrode or cathode electrode can be used as appropriate for the anode and / or the cathode, respectively, redundant description is omitted.

<Hole transport layer>
As the hole transport material constituting the hole transport layer, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, Triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thienylene vinylene) or And derivatives thereof.

  Among these hole transport materials, as the hole transport material, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, polyarylamine or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferable, and polyvinyl More preferred are carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, and the like. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  As a film formation method for the hole transport layer, a low molecular hole transport material can be formed by a film formation from a mixed solution with a polymer binder. A polymer hole transport material can be formed from a solution. There can be mentioned a method by film formation.

  In the step of producing the hole transport layer, first, a functional thin film (hole transport layer film) is formed, for example, by a coating method using a coating liquid containing a hole transport material.

  The coating liquid for the hole transport layer may be a solution or an emulsion. The solvent of the coating liquid for the hole transport layer may be any liquid that dissolves the hole transport material. For example, the solvents mentioned as the solvent for the coating liquid for the hole injection layer can be appropriately used, and the dispersion medium can be used. Any liquid that can uniformly disperse the hole transport material may be used.

  As a coating method, the coating methods mentioned as the coating method used for forming the hole injection layer and the organic EL light emitting layer described above can be appropriately used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those having low absorption of visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate (polymethyl acrylate, polymethyl methacrylate, etc.) polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the hole transport layer differs depending on the material used, and is selected so that the drive voltage and the light emission efficiency are appropriate, and at least a thickness that does not cause pin holes is required. If it is too high, the drive voltage of the element becomes high, which is not preferable. Therefore, the thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

<Electronic block layer>
The electron blocking layer is a layer having a function of blocking electron transport as described above. For example, in the case of an element configuration having a hole injection layer and an organic EL light emitting layer, the hole injection layer and the organic It means a layer (usually a hole transport layer) provided between the EL phosphor layer.

Specific examples of the layer structure of the organic EL device including the electron block layer are shown in the following q) to t).
q) Anode / electron block layer / organic EL phosphor layer / cathode r) Anode / hole transport layer / electron block layer / organic EL phosphor layer / cathode s) Anode / electron block layer / organic EL phosphor layer / electron Transport layer / cathode t) Anode / hole transport layer / electron blocking layer / organic EL phosphor layer / electron transport layer / cathode

  Examples of the electronic block material constituting the electronic block include polymers containing aromatic amines such as polyvinyl carbazole or derivatives thereof, polyarylene derivatives having aromatic amines in the side chain or main chain, arylamine derivatives, and triphenyldiamine derivatives. Illustrated.

  The method for forming the electron blocking layer is not limited. For example, when a polymer material is used, a method using film formation from a solution is exemplified.

  In the step of manufacturing the electronic block layer, first, a functional thin film (film for electronic block layer) is formed by a coating method using a coating solution containing an electronic block material, for example.

  The coating solution for the electronic block layer may be a solution or an emulsion. The solvent for the coating liquid for the electron block layer may be any liquid that dissolves the electron block material. For example, the solvents mentioned as the solvent for the coating liquid for the electron block layer can be used as appropriate. Any liquid that can uniformly disperse the block material may be used.

  As a coating method, the coating method mentioned as a coating method used for formation of the electronic block layer and the organic EL light emitting layer described above can be appropriately used.

  The coating solution for the electronic block layer may be a mixed solution with a polymer binder. As the polymer binder to be mixed, those not extremely disturbing the electronic block function are preferable, and those having weak absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate (polymethyl acrylate, polymethyl methacrylate, etc.), polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the electron block layer varies depending on the material used, and is selected so that the drive voltage and the light emission efficiency are appropriate. At least a thickness that does not cause pinholes is necessary, and is too thick. In such a case, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron blocking layer is, for example, 1 nm to 500 μm, preferably 2 nm to 200 nm, and more preferably 5 nm to 100 nm.

<Electron injection layer>
As an electron injecting material constituting the electron injecting layer, for example, an alkali metal, an alkaline earth metal, an alloy containing one or more of the above metals, an oxide of the above metal, a halogen, depending on the type of the organic EL light emitting layer And a mixture of the above substances. Examples of the alkali metal or its oxide, halide, carbonate include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, rubidium oxide, Examples include rubidium fluoride, cesium oxide, cesium fluoride, and lithium carbonate. Examples of alkaline earth metals or oxides, halides and carbonates thereof include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, barium fluoride, Examples include strontium oxide, strontium fluoride, and magnesium carbonate.

  The electron injection layer may be a laminate in which two or more layers are laminated. Specific examples of the laminate include LiF / Ca and the like. The electron injection layer is formed by vapor deposition, sputtering, printing, or the like. The thickness of the electron injection layer is preferably about 1 nm to 1 μm.

<Electron transport layer>
Examples of the electron transport material constituting the electron transport layer include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof. , Fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.

  Among these, as an electron transport material, an oxadiazole derivative, benzoquinone or a derivative thereof, anthraquinone or a derivative thereof, a metal complex of 8-hydroxyquinoline or a derivative thereof, a polyquinoline or a derivative thereof, a polyquinoxaline or a derivative thereof, a polyfluorene Or a derivative thereof is preferable, and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are further included. preferable.

  By using the organic EL element 1 described above, it is possible to realize a lighting apparatus including an organic EL element or a display apparatus including a plurality of organic EL elements.

  The organic EL element can be used as a backlight of a liquid crystal display device, an illumination device, a planar light source, a segment display device and a dot matrix display device, and the organic EL element itself emits linearly polarized light. In particular, it is suitably used as a backlight of a liquid crystal display device.

  When the organic EL element is used as a planar light source, for example, a planar anode and a cathode may be arranged so as to overlap each other when viewed from one side in the stacking direction. Further, in order to construct an organic EL element that emits light in a predetermined pattern as a light source of a segment display device, a method of installing a mask in which a light transmitting window is formed in a predetermined pattern on the surface of the planar light source, should be quenched There are a method in which the organic layer of the part is formed extremely thick so as not to emit light, and a method in which at least one of the anode and the cathode is formed in a predetermined pattern. By using these methods to form organic EL elements that emit light in a predetermined pattern, wiring is performed so that voltages can be selectively applied to several electrodes, thereby displaying numbers, letters, simple symbols, etc. A possible segment type display device can be realized.

  In order to use the light source of the dot matrix display device, the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other when viewed from one side in the stacking direction. In order to realize a dot matrix display device capable of partial color display and multi-color display, a method of separately coating a plurality of types of light emitting materials having different emission colors and a method using a color filter, a fluorescence conversion filter, and the like are used. Good. The dot matrix display device may be passively driven or may be actively driven in combination with a TFT or the like. These display devices can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, the planar light source is a self-luminous thin type and can be suitably used as a backlight of a liquid crystal display device or a planar illumination device. Further, by using a flexible substrate, it can be used as a curved light source or a display device.

  The backlight is configured by laminating the organic EL element formed in a planar shape and, for example, a diffusion plate. Further, the liquid crystal display device includes a liquid crystal cell, a pair of electrodes for applying an electric field to the liquid crystal cell, a pair of polarizing plates arranged with the liquid crystal cell interposed therebetween, and the backlight for irradiating one of the pair of polarizing plates with light. It is comprised including. In addition, when using an organic EL element with a high degree of polarization, the polarizing plate on the backlight side may be omitted from the pair of polarizing plates. As described above, since the organic EL element emits light polarized in a predetermined direction, the light emitted from the backlight is also polarized light. When such a backlight is used in a liquid crystal display device, a polarizing plate The loss of light at can be reduced. As a result, a liquid crystal display device with low power consumption can be realized.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The mass average molecular weight (Mw) of the polyorganosiloxane having an epoxy group and the [A] compound obtained in the following examples is a polystyrene conversion value measured by gel permeation chromatography (GPC) having the following specifications.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
In addition, the required amount of the raw material compound and the polymer used in the following examples was ensured by repeating the synthesis of the raw material compound and the polymer on the synthetic scale shown in the following synthesis examples as necessary.

<Synthesis of polyorganosiloxane having epoxy group>
[Synthesis Example 1]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were added. Charged and mixed at room temperature.
Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to give a polyorgano having an epoxy group. Siloxane was obtained as a viscous clear liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, a peak based on the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred. Mw of the obtained polyorganosiloxane having an epoxy group was 2,200, and the epoxy equivalent was 186.

<Synthesis of specific cinnamic acid derivatives>
All synthetic reactions of specific cinnamic acid derivatives were carried out in an inert atmosphere.
[Synthesis Example 2]
In a 500 mL three-necked flask equipped with a condenser tube, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide were mixed. Next, 7 g of acrylic acid was added to the mixed solution with a syringe and stirred. This mixed solution was further heated and stirred at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. The precipitate was recrystallized with a 1: 1 solution of ethyl acetate and hexane to obtain 8.4 g of a compound represented by the following formula (K-1) (specific cinnamic acid derivative (K-1)).

[Synthesis Example 3]
In a 300 mL three-necked flask equipped with a condenser, 6.5 g of 4-fluorophenylboronic acid, 10 g of 4-bromocinnamic acid, 2.7 g of tetrakistriphenylphosphine palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran, and 39 mL of pure water were mixed. Subsequently, the reaction solution was heated and stirred at 80 ° C. for 8 hours, and the completion of the reaction was confirmed by TLC. The reaction solution was cooled to room temperature, poured into 200 mL of 1N hydrochloric acid aqueous solution, and the precipitated solid was separated by filtration. The obtained solid was dissolved in ethyl acetate and subjected to liquid separation washing in the order of 100 mL of 1N hydrochloric acid aqueous solution, 100 mL of pure water, and 100 mL of saturated saline. Next, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was vacuum-dried to obtain 9 g of a compound represented by the following formula (K-2) (specific cinnamic acid derivative (K-2)).

[Synthesis Example 4]
In a 200 mL three-necked flask equipped with a condenser, 3.6 g of 4-fluorostyrene, 6 g of 4-bromocinnamic acid, 0.059 g of palladium acetate, 0.32 g of tris (2-tolyl) phosphine, 11 g of triethylamine, and 50 mL of dimethylacetamide. Mixed. This solution was heated and stirred at 120 ° C. for 3 hours, and after completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. By recrystallizing these precipitates with ethyl acetate, 4.1 g of a compound represented by the following formula (K-3) (specific cinnamic acid derivative (K-3)) was obtained.

[Synthesis Example 5]
Mixing 9.5 g of 4-vinylbiphenyl, 10 g of 4-bromocinnamic acid, 0.099 g of palladium acetate, 0.54 g of tris (2-tolyl) phosphine, 18 g of triethylamine, and 80 mL of dimethylacetamide in a 200 mL three-necked flask equipped with a condenser. did. This solution was heated and stirred at 120 ° C. for 3 hours, and after completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 500 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. By recrystallizing these precipitates with a 1: 1 solution of dimethylacetamide and ethanol, 11 g of a compound represented by the following formula (K-4) (specific cinnamic acid derivative (K-4)) was obtained.

［合成例６］
１Ｌのナス型フラスコに４−ヒドロキシ安息香酸メチル９１．３ｇ、炭酸カリウム１８２．４ｇ及びＮ−メチル−２−ピロリドン３２０ｍＬを仕込み、室温で１時間撹拌を行った後、１−ヨード−４，４，４−トリフロロブタン１１０．９ｇを加え１００℃で５時間撹拌した。反応終了後、水で再沈殿を行った。次いで、この沈殿に水酸化ナトリウム４８ｇ及び水４００ｍＬを加えて３時間還流して加水分解反応を行った。反応終了後、塩酸で中和し、生じた沈殿をエタノールで再結晶することにより４−（４，４，４−トリフルオロブチルオキシ）安息香酸の白色結晶を１０２ｇ得た。得られた４−ペンチルオキシ安息香酸のうち１０．４１ｇを反応容器中にとり、これに塩化チオニル１００ｍＬ及びＮ，Ｎ−ジメチルホルムアミド７７ｍＬを加えて８０℃で１時間撹拌した。続いて、減圧下で塩化チオニルを留去し、塩化メチレンを加えて炭酸水素ナトリウム水溶液で洗浄し、硫酸マグネシウムで乾燥し、濃縮を行った後、テトラヒドロフランを加えて溶液とした。次に、上記とは別の５００ｍＬ三口フラスコに４−ヒドロキシ桂皮酸７．３９ｇ、炭酸カリウム１３．８２ｇ、テトラブチルアンモニウム０．４８ｇ、テトラヒドロフラン５０ｍＬ及び水１００ｍＬを仕込んだ。この水溶液を氷冷し、上記テトラヒドロフラン溶液をゆっくり滴下し、さらに２時間撹拌下に反応を行った。反応終了後、塩酸を加えて中和し、酢酸エチルで抽出した後、硫酸マグネシウムで乾燥し、濃縮を行った後、エタノールで再結晶することにより、下記式（Ｋ−５）で表される化合物（特定桂皮酸誘導体（Ｋ−５））の白色結晶を９．２ｇ得た。

[Synthesis Example 6]
A 1-L eggplant-shaped flask was charged with 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate, and 320 mL of N-methyl-2-pyrrolidone, stirred at room temperature for 1 hour, and then 1-iodo-4,4. , 4-Trifluorobutane (110.9 g) was added and the mixture was stirred at 100 ° C. for 5 hours. After completion of the reaction, reprecipitation was performed with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate and refluxed for 3 hours to perform a hydrolysis reaction. After completion of the reaction, the reaction mixture was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 102 g of 4- (4,4,4-trifluorobutyloxy) benzoic acid white crystals. 10.41 g of the obtained 4-pentyloxybenzoic acid was placed in a reaction vessel, and 100 mL of thionyl chloride and 77 mL of N, N-dimethylformamide were added thereto, followed by stirring at 80 ° C. for 1 hour. Subsequently, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with an aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, concentrated, and then tetrahydrofuran was added to form a solution. Next, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran and 100 mL of water were charged into a 500 mL three-necked flask different from the above. The aqueous solution was ice-cooled, the tetrahydrofuran solution was slowly added dropwise, and the reaction was further performed with stirring for 2 hours. After completion of the reaction, the reaction mixture is neutralized by adding hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, concentrated, and recrystallized with ethanol to be represented by the following formula (K-5). 9.2 g of white crystals of the compound (specific cinnamic acid derivative (K-5)) were obtained.

<[A] Synthesis of photo-alignment compound>
[Synthesis Example 7]
In a 100 mL three-necked flask, 9.3 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 26 g of methyl isobutyl ketone, 3 g of the specific cinnamic acid derivative (K-1) obtained in Synthesis Example 2 above, and the trade name “ 0.10 g of “UCAT 18X” (a quaternary amine salt manufactured by San Apro Co., Ltd.) was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water three times, and then the solvent was distilled off to remove the [A] photo-alignment compound (S -1) was obtained as a white powder. [A] The mass average molecular weight Mw of the photo-alignment compound (S-1) was 3500.

[Synthesis Example 8]
The same procedure as in Synthetic Example 7 was performed except that 3 g of the specific cinnamic acid derivative (K-2) obtained in Synthetic Example 3 was used. As a result, 7.0 g of white powder of [A] photo-alignment compound (S-2) was obtained. [A] The mass average molecular weight Mw of the photo-alignment compound (S-2) was 4900.

[Synthesis Example 9]
The same procedure as in Synthesis Example 7 was carried out except that 4 g of the specific cinnamic acid derivative (K-3) obtained in Synthesis Example 4 was used. As a result, 10 g of white powder of [A] photo-alignment compound (S-3) was obtained. [A] The mass average molecular weight Mw of the photo-alignment compound (S-3) was 5000.

[Synthesis Example 10]
The same procedure as in Synthetic Example 7 was performed except that 4.1 g of the specific cinnamic acid derivative (K-4) obtained in Synthetic Example 5 was used. As a result, 10 g of white powder of [A] photo-alignment compound (S-4) was obtained. [A] The mass average molecular weight Mw of the photo-alignment compound (S-4) was 4200.

[Synthesis Example 11]
In a 200 mL three-necked flask, 5.0 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 46.4 g of methyl isobutyl ketone, and 5.3 g of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 6 ( It corresponds to 50 mol% with respect to the silicon atom of the polyorganosiloxane having an epoxy group.), And the photosensitizing compound is represented by the following formula (H-1-1)

1.08 g of the compound represented by the formula (corresponding to 20 mol% with respect to the silicon atom of the polyorganosiloxane having an epoxy group) and 0.10 g of tetrabutylammonium bromide were added and stirred at 80 ° C. for 12 hours. Reaction was performed. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water three times, and then the solvent was distilled off to remove the [A] photo-alignment compound (S -5 g of -5) was obtained as a white powder. [A] The mass average molecular weight Mw of the photo-alignment compound (S-5) was 12,500.

[Synthesis Example 12]
After dissolving 13.1 g of poly (2-hydroxyethyl methacrylate) in 50 ml of N-methyl-2-pyrrolidone and cooling to room temperature, 10 ml of pyridine was added. To this, 17.0 g of cinnamoyl chloride was added and stirred for 8 hours. The reaction mixture was diluted with N-methyl-2-pyrrolidone and added to methanol, and the precipitate was sufficiently washed with water and dried to obtain 25 g of [A] photo-alignment compound (S-6).

<[B] Synthesis of ester structure-containing compound>
An ester structure-containing compound (B-1-1) was synthesized according to the following scheme.

[Synthesis Example 13]
A 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube was charged with 21 g of trimesic acid, 60 g of n-butyl vinyl ether and 0.09 g of phosphoric acid, and reacted at 50 ° C. with stirring for 30 hours. After completion of the reaction, the organic layer obtained by adding 500 mL of hexane to the reaction mixture was separated and washed successively with 1M aqueous sodium hydroxide solution twice and water three times. Then, 50g of ester structure containing compounds (B-1-1) were obtained as a colorless and transparent liquid by distilling a solvent off from an organic layer.

<Preparation of composition for controlling orientation of organic EL phosphor>
[Example 1]
In a solvent having a composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio), 100 parts by mass of [A] photoalignable compound (S-1) obtained in Synthesis Example 7 was dissolved. It was set as the solution whose solid content concentration is 4.0 mass%. This solution was filtered with a filter having a pore diameter of 1 μm to prepare an organic EL phosphor alignment control composition (A-1).

[Examples 2 to 5]
[A] Various organic EL light emitter alignment control compositions (A-2) to (A-5) were prepared in the same manner as in Example 1 by changing the photoalignment compound. In Example 4, 5 parts by mass of the ester structure-containing compound (B-1-1) obtained in Synthesis Example 12 was further added to 100 parts by mass of the [A] compound to control the orientation of the organic EL phosphor. Composition (A-4) was prepared. These formulations are shown in Table 1.

Example 6
[A] N-methyl-2-pyrrolidone and butyl cellosolve are added to the photo-alignment compound (S-6), and the solvent composition is N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio), solid content concentration Was 4.0% by mass. This solution was filtered with a filter having a pore size of 1 μm to prepare an organic EL phosphor alignment control composition (A-6).

[Comparative Example 1]
1.00 g of 4- (2-methacryloyloxyethoxy) azobenzene, 0.01 g of 2,2′-azobis (isobutyronitrile) and 2.00 g of dried benzene were put in an ampule and deaerated, and then sealed. This was poured into methanol to obtain a polymer compound precipitate. After filtering this, the operation of dissolving the precipitate in benzene, reprecipitating with methanol and filtering was repeated twice and then dried. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to obtain a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio) and a solid content concentration of 4.0% by mass. The solution (CA-1) was prepared by filtering this solution through a filter having a pore size of 1 μm.

<Formation of Organic EL Luminor Orientation Control Film and Creation of Organic EL Element>
A glass substrate (sheet resistance 15Ω / □) coated with ITO as an anode electrode was ultrasonically cleaned with isopropyl alcohol, then with pure water, rinsed with isopropyl alcohol, and immediately dried. On the substrate on which the anode electrode was formed, the organic EL phosphor alignment control composition (A-1) prepared in Example 1 was applied with a spinner and prebaked for 1 minute on an 80 ° C. hot plate, The inside of the chamber was heated (post-baked) at 200 ° C. for 1 hour in an oven substituted with nitrogen to form a coating film having a thickness of 0.1 μm. The spinner rotation speed was 2000 rotations and the solid content concentration of the alignment control film solvent was 4.0 mass% so that the film thickness after formation was 0.1 μm. Next, the surface of the coating film was irradiated with a linearly polarized ultraviolet ray containing a 313 nm emission line perpendicularly from the substrate normal line using a Hg—Xe lamp and a Glen Taylor prism to form an organic EL light emitter alignment control film. The amount of light irradiation required for the orientation of the photoalignable group in the coating film formed at this time was measured and used as an index of the photoalignment sensitivity. The orientation of the photoalignable group was confirmed using a polarizing microscope.

Next, the substrate on which the orientation control film was applied was introduced into a substrate holder in a vacuum chamber and evacuated to 10 ⁻⁵ Pa. The evaporation cell is heated, and a trans-trans isomer of a styryl stilbene derivative represented by the following formulas (7-1) to (7-5) is co-deposited as a phosphor molecule on the organic EL phosphor alignment control film to form an organic EL. A phosphor layer (thickness 50 nm) was produced.

  Molar composition ratio formula (7-1): formula (7-2): formula (7-3): formula (7-4): formula (7-5) is approximately 1: 2: 2: 3: 2. . At this time, the substrate temperature was set to 25 ° C.

  Next, Mg and Ag were co-evaporated to produce a cathode electrode (thickness 50 nm, Mg: Ag = 10: 1 weight ratio), and an organic EL device having the structure shown in FIG. 1 was obtained.

  Organic EL elements were similarly prepared for the compositions prepared in Examples 2 to 6 and Comparative Example 1. These organic EL elements were evaluated by the following methods. The evaluation results are shown in Table 1.

<Evaluation of organic EL element>
(1) Evaluation of initial luminous efficiency The organic EL device produced by the above procedure is caused to emit light by a direct current of 10 mA / cm ² , the polarizing axis of the polarizing plate is arranged in parallel to the orientation direction of the phosphor molecules, and the polarizing plate is passed through. The luminous efficiency (polarized luminous efficiency) (Cd / A) was measured as the initial luminous efficiency.

(2) Evaluation of luminous efficiency after thermal load The organic EL element was placed under heating conditions, and the luminous efficiency after thermal load was measured to evaluate the stability against heat. Specifically, the organic EL device produced by the above procedure is heated in an oven set at 70 ° C. for 500 hours, and then light emission after thermal load is performed by the same procedure as “(1) Evaluation of initial luminous efficiency”. Efficiency was measured. The evaluation results are shown in Table 1. In addition, Table 1 shows the maintenance efficiency of the luminous efficiency after the heat load.

As is clear from the results in Table 1, according to the organic EL light emitter alignment control compositions of Examples 1 to 6, the light necessary for photo-alignment when an organic EL light emitter alignment control film is produced using these compositions. The irradiation amount was very low and the photoalignment sensitivity was good. In addition, the organic EL element provided with the alignment control film achieves high polarized light emission efficiency, and the organic EL element maintains a high ratio of the original light emission efficiency even after heat load, and has excellent heat resistance. Was obtained. In particular, it can be seen that the alignment films prepared using the organic EL light emitter alignment control compositions of Examples 1 to 5 have a very small decrease in issue efficiency after heat addition and excellent heat resistance. The alignment film produced using the composition of Comparative Example 1 required 20000 J / m ² as the light irradiation amount for photo-alignment. Further, in Comparative Example 1, in addition to the polarization emission efficiency being significantly lower than the polarization emission efficiency of the organic EL element of the example, the emission efficiency after thermal load is also greatly reduced, The result was inferior in heat resistance.

  Since the composition for controlling the alignment of organic EL light emitters of the present invention contains a compound having a photoalignable group containing a cinnamic acid structure, as described above, the photoalignment sensitivity is good and after heat load. In the organic EL element having excellent stability of the luminous efficiency and having the organic EL light emitter alignment control film, the anisotropic orientation of the organic EL light emitter is high due to the photo-alignment group on the surface of the organic EL light emitter alignment control film. Can be induced at the level, and as a result, excellent polarized light emission efficiency can be achieved.

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Substrate 3 Anode electrode 4 Organic EL light emitter orientation control film 5 Organic EL light emitter layer 6 Cathode electrode

Claims (6)

[A] a compound having a photoalignable group containing a cinnamic acid structure,
It said [A] compound,
At least one selected from the group consisting of a polyorganosiloxane containing a monovalent organic group having an epoxy group, a hydrolyzate thereof and a condensate of the hydrolyzate;
A compound represented by the following formula (1):
The organic EL emitter for alignment control composition is polyorganosiloxane compound is a reaction product.

(In the formula (1), R ¹ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group, or a part or all of hydrogen atoms of these phenylene group, biphenylene group, terphenylene group or cyclohexylene group. R ² is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, —CH═CH—, —NH— or —COO—, where a is , 1 to 3 and when a is 2 or more, the plurality of R ¹ and the plurality of R ² may be the same or different, R ³ is a fluorine atom or a cyano group, and b is 0 to 0. It is an integer of 4.) A monovalent organic group having an epoxy group is a compound represented by the following formula (X 1 _-1) or (X 1 _-2) organic EL emitter alignment control composition according to claim 1, which is represented by.

(In the formula (X ₁ -1), A is an oxygen atom or a single bond. H is an integer of 1 to 3, i is an integer of 0 to 6. However, when i is 0, A is It is a single bond.
Wherein _(X 1 -2), j is an integer from 1 to 6.
In the formulas (X ₁ -1) and (X ₁ -2), “*” represents a bond. ) [B] at least one structure selected from the group consisting of an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a t-butyl ester structure of a carboxylic acid. The composition for organic EL light emitter alignment control according to claim 1 or 2 , further comprising a compound having at least one. An organic EL light emitter alignment control film formed from the organic EL light emitter alignment control composition according to claim 1 , claim 2 or claim 3 . An anode electrode formed on the substrate;
The organic EL light emitter orientation control film according to claim 4 formed so as to cover the anode electrode,
An organic EL light emitter layer formed on the organic EL light emitter orientation control film;
An organic EL device comprising: a cathode electrode formed on the organic EL light emitting layer. A step of forming a coating film using the organic EL light emitter orientation control composition according to claim 1, 2 or 3 so as to cover the anode electrode formed on the substrate;
Irradiating the coating film with linearly polarized light to form an organic EL phosphor alignment control film,
The manufacturing method of the organic EL element which has the process of forming an organic EL light-emitting body layer on the said organic EL light-emitting body orientation control film, and the process of forming a cathode electrode on the said organic EL light-emitting body layer.

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