CN102079876B - Organic semiconductor orientation composition, organic semiconductor orientation film, organic semiconductor element and method for manufacturing same - Google Patents

Abstract

The invention relates to a composition for organic semiconductor alignment, an organic semiconductor alignment film, an organic semiconductor element and a manufacturing method thereof. The object of the present invention is to provide a kind of composition for organic semiconductor alignment that can form organic semiconductor alignment film, and the photo-alignment sensitivity of this alignment film is good, can realize the stability of carrier mobility from high heat resistance, can simultaneously It exhibits excellent carrier mobility by aligning organic semiconductor molecules in different directions at a high level. The present invention is a composition for organic semiconductor alignment comprising [A] a polyorganosiloxane compound having a photo-alignment group. The above photo-alignment group is preferably a group having a cinnamic acid structure. The above-mentioned group having a cinnamic acid structure is at least one selected from the group consisting of a group derived from a compound represented by the following formula (1) and a group derived from a compound represented by (2).

Description

Composition for organic semiconductor alignment, organic semiconductor alignment film, organic semiconductor element, and manufacturing method thereof

technical field

The present invention relates to an organic semiconductor alignment composition suitable as a composition for forming an organic semiconductor alignment film, an organic semiconductor alignment film formed from the composition, an organic semiconductor element having the organic semiconductor alignment film, and a method for producing the same. the

Background technique

In recent years, liquid crystal display elements are suitable for use in a wide range of applications ranging from small liquid crystal display devices such as mobile phones to large-screen liquid crystal display devices such as liquid crystal televisions due to their advantages of low power consumption and ease of miniaturization and flat panelization. In such a liquid crystal display element, an image can be displayed by switching the liquid crystal allocated to each dot on and off, and a thin film transistor (TFT) is used for switching the liquid crystal on and off. the

As semiconductor devices typified by field effect TFTs, inorganic semiconductors such as silicon are widely used, and organic semiconductors are being developed. Organic semiconductors include low-molecular-weight organic semiconductors and high-molecular-weight organic semiconductors. As materials constituting them, low-molecular-weight organic semiconductors that have been widely studied are pentacene, and high-molecular-weight organic semiconductors are polythiophene derivatives. Low-molecular-weight organic semiconductors form semiconductor layers by vapor deposition. In contrast, high-molecular organic semiconductors can form semiconductor layers by coating methods (centrifugal casting, inkjet methods, printing methods, etc.) without using vacuum and high-temperature processes. , but a process that can be coated at room temperature in the atmosphere, so it has the advantage of being able to be manufactured at low cost. In addition, it is expected to be formed on a resin substrate, so in addition to TFT, it is also expected to be used in various fields such as flexible displays, electronic paper, plastic IC cards, organic EL, and solar cells. the

In order to achieve higher performance of organic semiconductors, switching TFTs, for example, require a high operating frequency (for example, about several hundred kHz) and a high ratio of ON current/OFF current (ON/OFF ratio. For example, 10 ⁴ to 10 ⁶ about). In order to exhibit such a function, it is effective to control the drain current between the source and the drain. Here, the drain current (Id) in the saturation region satisfies the following relational expression (I).

Id=(W/2L)μCi(Vg-Vt) ² ...(I)

(In the formula, W represents the channel width, L represents the channel length, μ represents the carrier mobility, Ci represents the capacitance of the gate insulating film per unit area, Vg represents the gate voltage, and Vt represents the gate threshold voltage.)

Therefore, W/2L and Ci can be increased in order to meet the above-mentioned requirements, but if the former W/2L is increased, high-precision electrode patterns must be formed, resulting in a high cost. On the other hand, if the latter Ci is increased, the electrical conductivity of the gate insulating film will increase, and the film thickness must be reduced. From the viewpoint of preventing defects such as pinholes in a large-area process, there is a great limitation. Therefore, a method of increasing the degree of mobility μ of carriers focusing on such a small restriction has been gradually developed. As a specific method of increasing the degree of carrier mobility μ, it is attempted to increase the overlap of π orbitals (π electrons) that contribute to electrical conduction by introducing an alignment film that regulates the orientation of organic semiconductor molecules to align organic semiconductor molecules in a predetermined direction. , to increase carrier mobility. the

The relationship between the overlap of π orbitals caused by the orientation of organic semiconductor molecules and carrier movement can be considered as follows. In the case of π-electron conjugated polymers constituting high-molecular organic semiconductors, the polymer chains of the organic semiconductors are oriented in the same direction as the orientation direction of the alignment film (the direction between the electrodes), and thus may proceed toward the orientation direction of the main chain. Carriers move. In addition, in low-molecular-weight organic semiconductors, since π stacks of organic semiconductor molecules are formed in a direction (direction between electrodes) that forms a right angle to the orientation direction of the alignment film, it is possible to carry in a direction in which π orbitals overlap. The flow moves. the

Although the orientation of organic semiconductor molecules includes rubbing the organic semiconductor layer in the direction of carrier movement to increase anisotropy, it still cannot meet the requirements for plane overlap of π orbitals, or there is concern about frictional damage or contamination. In order to solve the problems of this rubbing method, a non-contact photo-alignment method has been developed. As an organic transistor using this photo-alignment method, for example, in Japanese Patent Laid-Open No. 2009-289783, in an embodiment, it is proposed to sequentially form a substrate, a gate, a gate insulating layer, an alignment layer, a source electrode and a drain electrode, and Organic field-effect transistors that contain organic semiconductor layers of specific materials. the

However, although the organic transistor of the above-mentioned document can obtain a certain degree of carrier mobility, it requires a light irradiation amount corresponding to the alignment of the photo-alignment group, and it cannot be considered that the photo-alignment sensitivity is sufficiently high. In addition, when trying to apply organic semiconductors to various fields, it is necessary to have weather resistance (heat resistance) that can maintain a high proportion of the original carrier mobility even under severe usage conditions such as high temperature. However, in the above-mentioned documents, no consideration is given to the heat resistance (carrier mobility stability) required as an alignment layer in an organic semiconductor device. the

In view of this situation, it is desired to develop an organic semiconductor alignment film that has good photo-alignment sensitivity, has carrier mobility stability due to high heat resistance, and can realize high-level alignment of organic semiconductor molecules at the same time. The high carrier mobility caused by the orientation in different directions; and the development of an organic semiconductor alignment composition that can form the organic semiconductor alignment film. the

【Existing technical literature】

【Patent Literature】

[Patent Document 1] Japanese Unexamined Patent Publication No. 2009-289783

Contents of the invention

The present invention is proposed based on the above-mentioned problems, and its purpose is to provide an organic semiconductor alignment film, which has good photo-orientation sensitivity, can realize the stability of carrier mobility due to high heat resistance, and can play a role at the same time. To make organic semiconductor molecules align in different directions at a high level to exert excellent carrier mobility; and to provide an organic semiconductor alignment composition capable of forming the organic semiconductor alignment film, an organic semiconductor element having the above-mentioned organic semiconductor alignment film, and The manufacturing method of this organic semiconductor element. the

The invention proposed in order to solve the said subject is the composition for organic semiconductor alignment containing [A] the polyorganosiloxane compound which has a photo-alignment group. the

Since the organic semiconductor alignment composition contains [A] a polyorganosiloxane compound having a photo-alignment group, when it is used to form an organic semiconductor alignment film, due to good photo-alignment sensitivity, the photo-alignment group can be reduced. The amount of light irradiation necessary for group orientation can be reduced, thereby improving the production efficiency of organic semiconductor devices. In addition, in the organic semiconductor alignment film formed using the organic semiconductor alignment composition, the organic semiconductor molecules can be aligned at a high level in different directions by [A] polyorganosiloxane compounds having photo-alignment groups. directional orientation, whereby excellent carrier mobility can be achieved in organic semiconductor elements. In addition, since the [A] polyorganosiloxane compound having a photo-alignment group of the organic semiconductor alignment composition uses polyorganosiloxane as the main chain, the thermal stability and chemical stability of the alignment film obtained High, showing high heat resistance, whereby the original carrier mobility can be maintained at a high ratio for a long time even after being heated. the

In the composition for aligning organic semiconductors, the photo-alignment group is preferably a group having a cinnamic acid structure. By using a group having a cinnamic acid structure with cinnamic acid or its derivatives as the basic skeleton as a photo-alignment group, high anisotropy can be given to the orientation of the organic semiconductor molecules caused by the obtained organic semiconductor alignment film, and further Improve carrier mobility in organic semiconductors. the

In the composition for aligning organic semiconductors, the above-mentioned group having a cinnamic acid structure is preferably a group consisting of a group derived from a compound represented by the following formula (1) and a group derived from a compound represented by (2) (hereinafter, one or both of the compound represented by the following formula (1) and the compound represented by the following formula (2) will be simply referred to as "specific cinnamic acid derivatives"). the

In formula (1), R ₁ is phenylene, biphenylene, terphenylene or cyclohexylene, a part of the hydrogen atom of this phenylene, biphenylene, terphenylene or cyclohexylene Or all of them 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 0-4.

In formula (2), R ₄ is phenylene or cyclohexylene, and a part or all of the hydrogen atoms of the phenylene or cyclohexylene can be replaced by a chain or cyclic alkyl group with 1 to 10 carbon atoms. , a chain 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 0-4. R ₇ is an oxygen atom, -COO-* or -OCO-* (wherein, in the above, the linkage with "*" is linked to R ₈ ). R ₈ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group. R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -* (wherein, in the above, the linkage with "*" is connected to the carboxyl group. f and g are 1 An integer of ∼10, e is an integer of 0∼3.

By using a group derived from the above-mentioned specific cinnamic acid derivative as the group having the above-mentioned cinnamic acid structure, the performance of imparting anisotropy to the organic semiconductor molecule, that is, the orientation performance can be further improved, and the π electrons of the organic semiconductor molecule can be easily fixed. conjugation or stacking, so as to further improve the carrier mobility of the organic semiconductor layer. the

In this organic semiconductor alignment composition, [A] the polyorganosiloxane compound having a photo-alignment group is preferably a polyorganosiloxane having an epoxy group, its hydrolyzate, and a condensate of its hydrolyzate A reaction product of at least one selected from the group consisting of at least one selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2). In this composition for aligning organic semiconductors, by utilizing the reactivity between polyorganosiloxane having epoxy groups and specific cinnamic acid derivatives, it is possible to introduce polyorganosiloxane having photo-alignment property into the main chain polyorganosiloxane. side chain groups of specific cinnamic acid derivatives. the

In the composition for aligning organic semiconductors, the 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 1-3, and i is an integer of 0-6. Wherein, when i is 0, A is a single bond.

In formula (X ₁ -2), j is an integer of 1-6.

In the formulas (X ₁ -1) and (X ₁ -2), "*" respectively represent a connecting bond.

By using the epoxy group represented by the above-mentioned formula (X ₁ -1) or (X _1-2 ) as the above-mentioned epoxy group, the polyorganosiloxane from the above-mentioned organic semiconductor alignment composition can be easily introduced. Side chain groups of specific cinnamic acid derivatives.

The organic semiconductor alignment composition preferably further contains [B] having two or more carboxylic acid acetal ester structures, carboxylic acid ketal ester structures, carboxylic acid 1-alkylcycloalkyl ester structures, and carboxylic acid A compound of at least one structure selected from the group consisting of tert-butyl ester structures. The composition for aligning organic semiconductors contains the compound (hereinafter referred to simply as "ester-structure-containing compound") containing such [B] component, and in the firing process (hereinafter referred to as "post-baking") after exposure, An acid is generated, and the cross-linking of the polyorganosiloxane compound having a photo-alignment group can be promoted through the generated acid, thereby improving the heat resistance of the obtained organic semiconductor alignment film. the

It is preferable that the composition for organic semiconductor alignment further contains [C] at least one polymer selected from the group consisting of polyamic acid and polyimide. the

By further containing [C] at least one polymer selected from the group consisting of polyamic acid and polyimide, the organic semiconductor alignment composition can exhibit a high insulation. In addition, in the formed organic semiconductor alignment film, since the polyorganosiloxane compound having a photo-alignment group that contributes to the anisotropic alignment of the organic semiconductor molecules exists near the surface of the alignment film, light passes through the alignment film. With the alignment group, organic semiconductor molecules can be anisotropically aligned at a high level, so that excellent carrier mobility can be achieved in organic semiconductor elements. the

In the composition for aligning organic semiconductors, the above-mentioned polyamic acid and polyimide are preferably a group consisting of aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. The reaction product of at least one tetracarboxylic dianhydride selected from among and at least one diamine selected from the group consisting of aliphatic diamine, alicyclic diamine and aromatic diamine. When the above-mentioned polyamic acid and polyimide are polymers obtained by such monomers, the electrical properties represented by insulation of the obtained organic semiconductor alignment film can be further improved. the

The organic semiconductor alignment film of the present invention is formed from the composition for organic semiconductor alignment. As a result, the organic semiconductor alignment film exhibits excellent carrier mobility stability due to high heat resistance even when heated, while easily defining the π-electron conjugation plane of the organic semiconductor molecule due to the photo-alignment group Or π-stacking orientation, excellent carrier mobility can be found in organic semiconductor layers. In addition, when the composition for organic semiconductor alignment contains [C] at least one polymer selected from the group consisting of polyamic acid and polyimide, the organic semiconductor alignment film can exhibit high insulation . the

In the organic semiconductor alignment film of the present invention, groups having a cinnamic acid structure are preferably unevenly distributed within a range from the surface to 30% of the film thickness. The group having a cinnamic acid structure that contributes to the orientation of the organic semiconductor can more effectively induce the orientation of the organic semiconductor molecules by distributing non-uniformly in the vicinity of the surface of the alignment film on the organic semiconductor side within the above-mentioned range. the

The organic semiconductor element of the present invention includes a gate formed on a substrate, an insulating film formed to cover the gate, an organic semiconductor alignment film formed on the insulating film by the organic semiconductor alignment composition, and an organic semiconductor alignment film formed on the above-mentioned organic semiconductor alignment film. The source and drain electrodes formed above, and the organic semiconductor layer formed at least between the source electrodes and the drain electrodes. Since the organic semiconductor element adopts the alignment film formed by the organic semiconductor alignment composition as the alignment film for the organic semiconductor, it can exhibit excellent photo-alignment sensitivity, reduce the amount of light irradiation, and simultaneously increase the load in the organic semiconductor layer. Mobility of streamers. Thus, in an organic semiconductor element, a high operating frequency and a high ON/OFF ratio can be realized. In addition, since the alignment film formed from this organic semiconductor alignment composition has high heat resistance, it can maintain the original carrier mobility for a long time even after being heated. the

The method for manufacturing an organic semiconductor element of the present invention includes an insulating film forming step of forming an insulating film to cover a gate formed on a substrate; and a coating film forming step of forming a coating film on the insulating film with the organic semiconductor alignment composition. an electrode forming process of forming a source electrode and a drain electrode on the above-mentioned coating film; and an organic semiconductor layer forming process of forming an organic semiconductor layer at least between the above-mentioned source electrode and the drain electrode; before the above-mentioned organic semiconductor layer forming process, it may further have A step of forming an organic semiconductor alignment film by irradiating linearly polarized light on the coating film. By employing the manufacturing method of the semiconductor element, the organic semiconductor element can be efficiently and simply manufactured. the

The organic semiconductor element of the present invention includes a gate formed on a substrate, an organic semiconductor alignment film for covering the gate formed by the organic semiconductor alignment composition containing [C] component, on the organic semiconductor alignment film A source electrode and a drain electrode are formed, and an organic semiconductor layer is formed at least between the source electrode and the drain electrode. Since the organic semiconductor element adopts an alignment film formed of the organic semiconductor alignment composition containing [C] component as a so-called gate insulating film, excellent insulation can be exhibited, and at the same time, the organic semiconductor layer can be improved. Carrier mobility, so that high operating frequency and high ON/OFF ratio can be realized in organic semiconductor devices. the

The method for producing an organic semiconductor element of the present invention includes a coating film forming step of forming a coating film to cover a gate formed on a substrate with the organic semiconductor alignment composition; and an electrode forming step of forming a source electrode and a drain electrode on the coating film. and at least an organic semiconductor layer forming process for forming an organic semiconductor layer between the above-mentioned source and drain electrodes; before the above-mentioned organic semiconductor layer forming process, it may further have a process of irradiating linearly polarized light to the above-mentioned coating film to form an organic semiconductor alignment film . By employing the manufacturing method of the semiconductor element, the organic semiconductor element can be efficiently and simply manufactured. the

As described above, according to the composition for organic semiconductor alignment, organic semiconductor alignment film, organic semiconductor element and manufacturing method thereof of the present invention, the sensitivity of photo-alignment is good, and the stability of carrier mobility is realized by high heat resistance, and at the same time Organic semiconductor molecules can be anisotropically aligned at a high level, and excellent carrier mobility can be exhibited. the

Description of drawings

FIG. 1 is a cross-sectional view schematically showing an example of an organic semiconductor device of the present invention. the

FIG. 2 is a cross-sectional view schematically showing an example of the organic semiconductor device of the present invention. the

FIG. 3 is a graph showing the distribution in the film thickness direction of fragments of m/z=231 observed by TOF-SIMS in Example 14. FIG. the

FIG. 4 is a graph showing the cumulative value of presence in the film thickness direction of a segment of m/z=231 observed by TOF-SIMS in Example 14. FIG. the

Detailed ways

Since the organic semiconductor alignment composition of the present invention contains [A] a polyorganosiloxane compound having a photo-alignment group (hereinafter, simply referred to as a "photo-alignment polyorganosiloxane compound"), it can pass high-sensitivity polyorganosiloxane compounds. The photo-orientation property reduces the amount of light irradiation necessary for alignment. In addition, due to the use of the composition for organic semiconductor alignment, the obtained organic semiconductor alignment film exhibits high heat resistance, and thus can exhibit high carrier mobility stability after being heated. In addition, the organic semiconductor alignment film is due to It has excellent photo-orientation, so it can exhibit a high level of anisotropic orientation in the organic semiconductor layer. the

The organic semiconductor alignment composition may contain [A] a photo-alignment polyorganosiloxane compound, [B] an ester-containing compound, and/or [C] a polyamic acid and At least one polymer selected from the group consisting of polyimides may also contain, as an optional component, polymers other than photo-alignment polyorganosiloxane compounds (hereinafter referred to as "other polymers"). ”), curing agent, curing catalyst, curing accelerator, compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), functional silane compound, surfactant, photosensitizing compound wait. Hereinafter, this composition for organic semiconductor alignment is demonstrated. the

<[A] Component: Polyorganosiloxane compound having a photo-alignment group>

For [A] the polyorganosiloxane compound having a photo-alignment group, selected from the group consisting of polyorganosiloxane, its hydrolyzate, and condensate of its hydrolyzate as the main chain A photo-alignment group is introduced as a side chain on at least one of the moieties. When an organic semiconductor alignment film is formed using the composition for organic semiconductor alignment, if the photo-alignment group is irradiated with anisotropic light such as polarized light, in the organic semiconductor alignment film, rearrangement and Anisotropic chemical reactions, etc. By changing the molecular structure of the anisotropic alignment film, anisotropy can be imparted to organic semiconductor molecules. In addition, due to the photo-alignment group and the polyorganosiloxane compound, the sensitivity of photo-alignment is good, and a low light irradiation amount can be realized. At the same time, since polyorganosiloxane is used as the main chain, the organic semiconductor alignment film formed from the semiconductor alignment composition has excellent chemical stability and thermal stability, and exhibits high heat resistance, so even if heated After that, the carrier mobility can also be maintained for a long time. the

(photo-alignment group) 

As described above, the photo-alignment group induces a change in the microstructure of the molecules constituting the alignment film when irradiated with anisotropic light. Such a photo-alignment group is not particularly limited, and groups derived from various compounds showing photo-orientation can be used. Mechanisms showing anisotropy as a photo-alignment group are divided into two types: a photoreaction type and a photoisomerization type. The photoreactive type is further divided into dimerization type, decomposition type, binding type, and decomposition crosslinking type. From the viewpoint of not contaminating the organic semiconductor layer, a type in which impurity ions, radicals, etc. do not remain after light irradiation is preferred, so a photoisomerization type and a dimerization type are preferable. the

Specific examples of photo-alignment groups include azobenzene-containing groups containing azobenzene or derivatives thereof as a basic skeleton, groups having a cinnamic acid structure containing cinnamic acid or derivatives thereof as a basic skeleton, Groups, phenylacryloylbenzene-containing groups containing phenylacryloylbenzene or its derivatives as the basic skeleton, benzophenone-containing groups containing benzophenone or its derivatives as the basic skeleton, having coumarin A coumarin-containing group containing a polyimide or a derivative thereof as a basic skeleton, a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton, and the like. Among these photo-alignment groups, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable in consideration of exhibiting dimer anisotropy and ease of introduction of high alignment energy. In addition, cinnamic acid or its derivatives are not limited to cis-form or trans-form as long as they can be dimerized by light irradiation. the

The structure of the group having a cinnamic acid structure is not particularly limited as long as it contains cinnamic acid or a derivative thereof as a basic skeleton, but is preferably derived from a compound represented by the above formula (1) and a compound represented by the above formula (2) ( That is, a group of at least one of specific cinnamic acid derivatives). In addition, in the above-mentioned formula (1), R ₁ is phenylene, biphenylene, terphenylene or cyclohexylene, the hydrogen of the phenylene, biphenylene, terphenylene or cyclohexylene Some or all of the atoms 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 0-4.

As a compound represented by said formula (1), the following things are mentioned, for example. the

Among them, R ₁ is preferably an unsubstituted phenylene group or a phenylene group that may be substituted by a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and R ₂ is preferably a single bond, an oxygen atom, or -CH ₂ = _CH2- . b is preferably 0-1, and when a is 1-3, b is particularly preferably 0.

In the above formula (2), R ₄ is phenylene or cyclohexylene, and a part or all of the hydrogen atoms of the phenylene or cyclohexylene can be replaced by a chain or cyclic alkane with 1 to 10 carbon atoms. group, chain or cyclic alkoxy group with 1 to 10 carbon atoms, fluorine atom or 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 0-4. R ₇ is an oxygen atom, -COO-* or -OCO-* (wherein, in the above, the linkage with "*" is linked to R ₈ ). R ₈ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed ring group. R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -* (wherein, in the above, the linkage with "*" is connected to the carboxyl group. f and g are 1 An integer of ∼10, e is an integer of 0∼3.

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

In the above formula, Q is a chain or cyclic alkyl group with 1 to 10 carbon atoms, a chain or cyclic alkoxy group with 1 to 10 carbon atoms, a fluorine atom or a cyano group, f and the formula The definition in (2) is the same. the

(Synthesis of Specific Cinnamic Acid Derivatives) 

The synthesis procedure of a specific cinnamic acid derivative is not particularly limited, and conventionally known methods can be combined. As a representative synthesis procedure, for example, (1) under basic conditions, react a compound having a benzene ring skeleton substituted by a halogen atom with acrylic acid in the presence of a transition metal catalyst to obtain a specific cinnamic acid derivative Method; (2) under basic conditions, make the hydrogen atom of benzene ring be substituted by halogen atom cinnamic acid and the compound that has the benzene ring skeleton that is substituted by halogen atom, react in the presence of transition metal catalyst, form specific cinnamic acid Derivative methods, etc. However, the synthesis procedure of a specific cinnamic acid derivative is not limited to these methods. the

(a part derived from at least one selected from the group consisting of polyorganosiloxane, its hydrolyzate, and the condensate of its hydrolyzate)

At least one selected from the group consisting of polyorganosiloxane, its hydrolyzate, and the condensate of its hydrolyzate contained in the [A] photo-alignment polyorganosiloxane compound as a main chain The moiety is not particularly limited as long as it is a moiety derived from a structure capable of introducing the above-mentioned photo-alignment group itself. [A] The photo-alignment polyorganosiloxane compound contains this moiety derived from at least one selected from the group consisting of polyorganosiloxane, its hydrolyzate, and the condensate of its hydrolyzate, and A group of compounds that exhibit photo-alignment properties. the

As a structure which can introduce the said photo-alignment group, a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a mercapto group, an ester group, an amide etc. are mentioned, for example. Among them, an epoxy group is preferable in consideration of ease of introduction and preparation. the

[A] The polyorganosiloxane compound having a photo-alignment group is preferably at least one selected from the group consisting of polyorganosiloxane having an epoxy group, its hydrolyzate, and the condensate of its hydrolyzate. (hereinafter also simply referred to as "polyorganosiloxane having an epoxy group"), and the reaction product of the compound represented by the above formula (1) and/or (2). In this organic semiconductor alignment composition, by utilizing the reactivity between polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, it is possible to easily introduce polyorganosiloxane having light into the main chain. Orientational groups derived from specific cinnamic acid derivatives. the

(polyorganosiloxane with epoxy group)

The polyorganosiloxane having an epoxy group used in the composition for aligning organic semiconductors is not particularly limited as long as an epoxy group is introduced into the polyorganosiloxane as a side chain. The above-mentioned polyorganosiloxane having an epoxy group is preferably selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (3), its hydrolyzate, and a condensate of its hydrolyzate. out at least one. the

In formula (3), X ₁ is a monovalent organic group having an epoxy group, Y ₁ is a hydroxyl group, an alkoxy group with 1 to 10 carbon atoms, an alkyl group with 1 to 20 carbon atoms, or a carbon atom An aryl group whose number is 6-20.

In addition, the hydrolysis condensate of the polyorganosiloxane having the repeating unit represented by the above formula (3) is not only the hydrolysis condensate between the polyorganosiloxanes, but also contains the polyorganosiloxane obtained by the above formula (3). Hydrolysis condensation of the repeating unit shown in the above-mentioned formula (3) when the polyorganosiloxane obtained has the repeating unit represented by the above formula (3) during the process of producing polyorganosiloxane, such as branching and crosslinking of the main chain. the concept of. the

_X 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 groups containing a glycidyl group, glycidyloxy group, epoxycyclohexyl group, etc. . This _X1 corresponds to the epoxy group of the above-mentioned polyorganosiloxane having an epoxy group. The above-mentioned epoxy group (that is, X ₁ ) is preferably represented by the above-mentioned formula (X _1-1 ) or (X _1-2 ). In addition, in the above-mentioned formula (X _1-1 ) or (X _1-2 ) Among the epoxy groups shown, groups represented by the following formula (X ₁ -1-1) or (X ₁ -2-1) are preferable.

In the above formula, "*" represents a connecting bond. the

In _Y1 in the above-mentioned formula (3), respectively, as the alkoxy group having 1 to 10 carbon atoms, for example, methoxy group, ethoxy group, etc.; as the alkoxy group having 1 to 20 carbon atoms For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-lauryl, n-dodecyl Alkyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like; examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and the like.

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, more preferably 1,000 to 10,000, and still more preferably 1,000 to 5,000. the

This polyorganosiloxane with epoxy group is preferably obtained by mixing a silane compound with an epoxy group, or a mixture of a silane compound with an epoxy group and other silane compounds, preferably in a suitable organic solvent, water and a catalyst. Existence, by hydrolysis or hydrolysis, condensation synthesis. the

Examples of the above-mentioned silane compound having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethyl Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and the like. the

Examples of other silane compounds mentioned above include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, Butoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorine Trichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, fluorotriisopropoxysilane, fluorotri-n-butoxysilane, fluorinated Tri-sec-butoxysilane, Methyltrichlorosilane, Methyltrimethoxysilane, Methyltriethoxysilane, Methyltri-n-propoxysilane, Methyltriisopropoxysilane, Methyltrimethoxysilane n-butoxysilane, methyltri-sec-butoxysilane, 2-(trifluoromethyl)ethyltrichlorosilane,

2-(Trifluoromethyl)ethyltrimethoxysilane, 2-(trifluoromethyl)ethyltriethoxysilane, 2-(trifluoromethyl)ethyltri-n-propoxysilane , 2-(trifluoromethyl)ethyltriisopropoxysilane, 2-(trifluoromethyl)ethyltri-n-butoxysilane, 2-(trifluoromethyl)ethyltri-secondary Butoxysilane, 2-(perfluoro-n-hexyl)ethyltrichlorosilane, 2-(perfluoro-n-hexyl)ethyltrimethoxysilane, 2-(perfluoro-n-hexyl)ethyltriethyl Oxysilane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxysilane, 2-(perfluoro-n-hexyl)ethyltriisopropoxysilane, 2-(perfluoro-n-hexyl)ethyl 2-(perfluoro-n-hexyl)ethyl tri-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)ethyltriisopropoxysilane, 2-(perfluoro-n-octyl)ethyl Tri-n-butoxysilane, 2-(perfluoro-n-octyl)ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, Hydroxymethyltri-n-propoxysilane, Hydroxymethyltriisopropoxysilane, Hydroxymethyltri-n-butoxysilane, Hydroxymethyltri-sec-butoxysilane, 3-(meth)acryloxy Propyltrichlorosilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloyl Oxypropyltri-n-propoxysilane, 3-(meth)acryloxypropyltriisopropoxysilane, 3-(meth)acryloxypropyltri-n-butoxysilane, 3 -(Meth)acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Mercaptopropyltri-n-propoxysilane, 3-Mercaptopropyltriisopropoxysilane, 3-Mercaptopropyltri-n-butoxysilane, 3-Mercaptopropyltri-sec-butoxysilane, Mercaptomethyl Trimethoxysilane,

Mercaptomethyltriethoxysilane, Vinyltrichlorosilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltri-n-Propoxysilane, Vinyltriisopropoxysilane, Ethylene Allyl tri-n-butoxysilane, vinyl tri-sec-butoxysilane, allyl trichlorosilane, allyl trimethoxysilane, allyl triethoxysilane, allyl tri-n-propoxy Silane, Allyltriisopropoxysilane, Allyltri-n-Butoxysilane, Allyltri-S-Butoxysilane, Phenyltrichlorosilane, Phenyltrimethoxysilane, Phenyltriethylsilane Oxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, methyldichlorosilane, methyldichlorosilane Methoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldiisopropoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, di Methyldichlorosilane, Dimethyldimethoxysilane, Dimethyldiethoxysilane, Dimethyldi-n-propoxysilane, Dimethyldiisopropoxysilane, Dimethyldi-n-propoxysilane Butoxysilane, dimethyldi-sec-butoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorosilane, (methyl)[2-(perfluoro-n- Octyl)ethyl]dimethoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxysilane, (methyl)[2-(perfluoro-n-octyl) )ethyl]di-n-propoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]diisopropoxysilane, (methyl)[2-(perfluoro-n-octyl) )ethyl]di-n-butoxysilane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-sec-butoxysilane, (methyl)(3-mercaptopropyl)dichloro Silane, (methyl)(3-mercaptopropyl)dimethoxysilane, (methyl)(3-mercaptopropyl)diethoxysilane, (methyl)(3-mercaptopropyl)di-n-propyl Oxysilane, (methyl)(3-mercaptopropyl)diisopropoxysilane, (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)diisopropoxysilane, (methyl)(vinyl)di-n-butoxysilane, (methyl)(ethylene base) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldiiso Propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane , Diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxy dimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromide trimethylsilane, iodide trimethylsilane, methoxytrimethylsilane butylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, isopropoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, tert-butoxy (Chloro)(vinyl)dimethylsilane, (methoxy)(vinyl)dimethylsilane, (ethoxy)(vinyl)dimethylsilane, (chloro )(methyl)diphenylsilane, (methoxy)(methyl)diphenylsilane, (ethoxy)(methyl)diphenylsilane and other silane compounds having one silicon atom, and

Indicated by trade name, examples include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21 -5845, X-21-5846, 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 -1053, 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 (above, manufactured by Shin-Etsu Chemical Co., Ltd.); Glas Resin (manufactured by Showa Denko Co., Ltd.); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405 , SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray Dou Corning Co., Ltd.); FZ3711, FZ3722 (above, manufactured by Japan Unicar Co., Ltd.); DMS-S12, 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 Chitsuso Co., Ltd.); Methill Sirike-to MS51, Metchel Sirike-to MS56 (above, manufactured by Mitsubishi Chemical Co., Ltd.); (above, manufactured by Colcoat Co., Ltd.); partial condensates such as GR100, GR650, GR908, GR950 (above, manufactured by Showa Denko Co., Ltd.). the

Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyltriethoxysilane are preferred from the viewpoint of the orientation and chemical stability of the obtained organic semiconductor alignment film. 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Allyltrimethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropyl Triethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane. the

The polyorganosiloxane having epoxy groups used in the present invention has an epoxy equivalent of preferably It is 100 to 10,000 g/mol, more preferably 150 to 1,000 g/mol. Therefore, when synthesizing a polyorganosiloxane having an epoxy group, it is preferable to set the use ratio of the silane compound having an epoxy group and other silane compounds so that the epoxy equivalent of the obtained polyorganosiloxane falls within the above-mentioned range. . the

Specifically, such other silane compounds are preferably used in an amount of 0 to 50% by mass, more preferably in an amount of 5 to 30% by mass, relative to the total amount of polyorganosiloxane having an epoxy group and other silane compounds. the

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

Respectively, examples of hydrocarbons include toluene, xylene, etc.; examples of the above-mentioned ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexyl Ketones and the like; Examples of the above-mentioned esters include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; Examples of the aforementioned ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; examples of the aforementioned alcohol include 1-hexanol, 4-methyl-2 - Pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono-n-propyl ether, etc. Among them, water-insoluble ones are preferable. These organic solvents can be used alone or in combination of two or more. the

The amount of the organic solvent used is preferably 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass, relative to 100 parts by mass of all the silane compounds. In addition, when producing polyorganosiloxane having an epoxy group, the amount of water used is preferably 0.5 to 100 times moles, more preferably 1 to 30 times moles, based on the persilane compound. the

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or the like can be used. the

As said alkali metal compound, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide etc. are mentioned, for example. the

As the above-mentioned organic bases, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole; triethylamine, tri-n-propylamine, tri-n-butyl tertiary organic amines such as base amine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide, etc. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine are preferred in view of stable reaction; tetramethyl hydroxide Organic quaternary ammonium salts such as ammonium. the

As a catalyst when producing 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 target polyorganosiloxane can be obtained at a high hydrolysis and condensation rate without side reactions such as ring opening of the epoxy group, so it is excellent in production stability and is preferably used . In addition, the organic semiconductor alignment composition of the present invention containing a reaction product of a polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, wherein the polyorganosiloxane is synthesized using an alkali metal compound or an organic base as a catalyst, Since the storage stability is extremely excellent, it is suitable. the

The reason is as pointed out in Chemical Reviews, volume 95, p1409 (1995), it is speculated that if 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 makes it impossible to obtain a polyorganosiloxane containing a small proportion of silanol groups. It is presumed that the condensation reaction between silanol groups is suppressed due to the low content ratio of silanol groups, and when the organic semiconductor alignment composition of the present invention contains other polymers described later, the silanol group and other polymers are suppressed. Condensation reaction, resulting in excellent storage stability. the

As catalysts, organic bases are particularly preferred. The amount of the organic base used varies depending on the type of the organic base, reaction conditions such as temperature, and the like, and can be appropriately set. The specific usage-amount of an organic base is, for example, preferably 0.01 to 3 times moles, more preferably 0.05 to 1 times moles with respect to all the silane compounds. the

The hydrolysis or hydrolysis and condensation reaction when producing the polyorganosiloxane having an epoxy group is preferably carried out by dissolving a silane compound having an epoxy group and other silane compounds used as needed in an organic solvent, and mixing the solution with an organic base Mix with water, by heating, eg in an oil bath. the

During the hydrolysis and condensation reactions, the heating temperature of the oil bath is preferably 130° C. or lower, more preferably 40 to 100° C., preferably for 0.5 to 12 hours, more preferably for 1 to 8 hours. When heating, the mixed solution can be stirred or left standing under reflux. the

After completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. In this washing, it is preferable to wash with water containing a small amount of salt, for example, about 0.2% by mass of ammonium nitrate aqueous solution, etc. in terms of easy washing operation. Washing is carried out until the washed water layer becomes neutral, and if necessary, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, and then the solvent is removed to obtain the target polyorganosiloxane having an epoxy group. the

In the present invention, commercially available ones can be used as the polyorganosiloxane having an epoxy group. Examples of such commercial products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chitsuso Co., Ltd.). the

[A] The photo-alignment polyorganosiloxane compound contains a part derived from the hydrolyzate produced by the hydrolysis of the polyorganosiloxane having an epoxy group itself, and a part derived from the hydrolysis condensation between polyorganosiloxanes having an epoxy group. Part of the hydrolysis condensate. These hydrolyzates or hydrolysis condensates which are constituent materials of this part are also prepared under the same conditions as the hydrolysis and condensation of epoxy group-containing polyorganosiloxane. the

([A] Synthesis of Polyorganosiloxane Compounds with Photo-Alignment Groups) 

The [A] polyorganosiloxane compound having a photo-alignment group used in the present invention can be obtained, for example, by combining the above-mentioned polyorganosiloxane with an epoxy group and the above-mentioned formula (1) and/or ( 2) The compounds shown in (ie, specific cinnamic acid derivatives) are preferably synthesized by reaction in the presence of a catalyst. the

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

As the catalyst, an organic base or a known compound known as a curing accelerator that accelerates the reaction between an epoxy compound and an acid anhydride can be used. the

As the above-mentioned organic base, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole can be listed;

Organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;

Organic quaternary ammonium like tetramethylammonium hydroxide etc. the

Among these organic bases, organic tertiary amines like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine are preferred; organic quaternary ammoniums like tetramethylammonium hydroxide Salt. the

As the above-mentioned curing accelerator, for example, tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, triethanolamine can be listed;

Like 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 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-bis(hydroxymethyl)imidazole, 1-(2-cyano Ethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium Trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium Onium 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, the isocyanuric acid adduct of 2-methylimidazole, the isocyanuric acid adduct of 2-phenylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-( 1')] imidazole compounds such as isocyanuric acid adducts of ethyl-s-triazine;

Organophosphorus compounds like diphenylphosphine, triphenylphosphine, triphenylphosphite;

Like benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Phosphonium, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorous dithiosulfate, tetra-n-butylphosphonium benzotri Quaternary phosphonium salts such as azolium salt, tetraphenylphosphonium tetraphenyl borate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenyl borate;

Diazobicycloalkenes such as 1,8-diazobicyclo[5.4.0]undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octoate, tin octoate, aluminum acetylacetonate complexes;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;

Boron compounds like boron trifluoride, triphenyl borate;

Metal halides like zinc chloride, tin chloride;

High melting point dispersive latent curing accelerators such as amine addition accelerators such as dicyanodiamide and adducts of amines and epoxy resins;

A microcapsule type latent curing accelerator formed by covering the surface of the curing accelerator such as the above-mentioned imidazole compound, organic phosphorus compound, and quaternary phosphonium salt with a polymer;

Amine salt type latent curing accelerator;

Latent curing accelerators such as pyrolysis-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salts and Bronsted acid salts, etc. the

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

The catalyst is preferably used in an amount of 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, based on 100 parts by mass of the polyorganosiloxane having an epoxy group. the

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

[A] The photo-alignment polyorganosiloxane compound can be synthesized in the presence of an organic solvent if necessary. Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Among them, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoint of solubility of raw materials and products, and easiness of product purification. The solid content concentration of the solvent (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass to 70% by mass, more preferably 5% by mass to 50% by mass use. the

The mass average molecular weight of the [A] photo-alignment polyorganosiloxane compound thus obtained in terms of polystyrene by gel permeation chromatography is not particularly limited, but is preferably 1,000 to 20,000, more preferably 3,000 to 15,000. By being within this molecular weight range, good orientation and stability of the organic semiconductor alignment film can be ensured. the

The above-mentioned [A] photo-alignment polyorganosiloxane compound introduces the polyorganosiloxane derived from the specific cinnamic acid derivative into the polyorganosiloxane having the epoxy group by the ring-opening addition of the carboxyl group of the specific cinnamic acid derivative to the epoxy group. the structure of the thing. This production method is simple and particularly suitable for increasing the rate of introduction of a structure derived from a specific cinnamic acid derivative. the

In the present invention, a part of the above-mentioned specific cinnamon derivative may be substituted with a compound represented by the following formula (4) within a range not impairing the effects of the present invention. In this case, [A] the photo-alignment polyorganosiloxane compound can be synthesized by making a polyorganosiloxane having an epoxy group, a specific cinnamic acid derivative and a compound represented by the following formula (4) The reaction of the mixture proceeds. the

R ₁₀ - R ₁₁ - R ₁₂ (4)

R ₁₀ in the above formula (4) is preferably an alkyl or alkoxy group having 8 to 20 carbon atoms, or a fluoroalkyl or fluoroalkoxy group having 4 to 21 carbon atoms. ₁₁ is preferably a single bond, 1,4-cyclohexylene or 1,4-phenylene, and R ₁₂ is preferably a carboxyl group.

As a preferable example of the compound represented by said formula (4), the compound represented by any one of following formula (4-1)-(4-3) is mentioned, for example. the

The compound represented by the above-mentioned formula (4) contributes to the inactivation of the active site of the [A] photo-alignment polyorganosiloxane compound, and improves the stability of the composition for aligning organic semiconductors. In the present invention, when the compound represented by the above formula (4) and the specific cinnamic acid derivative are used together, the total usage ratio of the specific cinnamic acid derivative and the compound represented by the above formula (4) is relative to 1 mol of polyorganic acid The epoxy group that siloxane has is preferably 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, and still more preferably 0.05 to 0.9 mol. In this case, the compound represented by the above formula (4) is preferably used in an amount of 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the specific cinnamic acid derivative. When the usage ratio of the compound represented by said formula (4) exceeds 50 mol%, there exists a possibility that the problem of the orientation reduction in an organic semiconductor alignment film may generate|occur|produce. the

<[B]Ingredient: compound containing ester structure>

The composition for organic semiconductor alignment can improve the storage stability of the composition for organic semiconductor alignment while forming an organic semiconductor alignment film excellent in heat resistance and light resistance by including the [B] ester-containing compound. the

[B] Compounds containing ester structures have two or more carboxylic acid acetal ester structures, carboxylic acid ketal ester structures, carboxylic acid 1-alkylcycloalkyl ester structures and carboxylic acid tertiary ester structures in the molecule. A compound of at least one structure selected from the group consisting of butyl ester structures. [B] The ester-containing compound may be a compound having two or more structures of the same type among these structures, or may be a compound having two or more structures combining different types of these structures. Examples of the acetal structure-containing group of the carboxylic acid include groups represented by the following formulas (B-1) and (B-2). the

In formula (B-1), R ₁₃ and R ₁₄ are each independently an alkyl group with 1 to 20 carbon atoms, an alicyclic group with 3 to 10 carbon atoms, an aromatic group with 6 to 10 carbon atoms. group or an aralkyl group with 7 to 10 carbon atoms,

In formula (B-2), n1 is an integer of 2-10. the

Wherein, for R ₁₃ in the above formula (B-1), they are:

As an alkyl group, preferably a methyl group;

As an alicyclic group, preferably a cyclohexyl group;

As aryl, preferably phenyl;

As aralkyl, benzyl is preferred;

The alkyl group of _R14 is preferably an alkyl group with 1 to 6 carbon atoms;

As the alicyclic group, it is preferably an alicyclic group with 6 to 10 carbon atoms;

As aryl, preferably phenyl;

The aralkyl group is preferably benzyl or 2-phenylethyl. As n1 in the formula (B-2), 3 or 4 is preferable. the

Examples of the group represented by the above formula (B-1) include 1-methoxyethoxycarbonyl, 1-ethoxyethoxycarbonyl, 1-n-propoxyethoxycarbonyl, 1 -Isopropoxyethoxycarbonyl, 1-n-butoxyethoxycarbonyl, 1-isobutoxyethoxycarbonyl, 1-sec-butoxyethoxycarbonyl, 1-tert-butoxyethyl Oxycarbonyl, 1-cyclopentyloxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 1-norbornyloxyethoxycarbonyl, 1-bornyloxyethoxycarbonyl, 1-phenoxyethoxycarbonyl, 1-(1-naphthyloxy)ethoxycarbonyl, 1-benzyloxyethoxycarbonyl, 1-phenethyloxyethoxycarbonyl, (ring Hexyl)(methoxy)methoxycarbonyl, (cyclohexyl)(ethoxy)methoxycarbonyl, (cyclohexyl)(n-propoxy)methoxycarbonyl, (cyclohexyl)(isopropoxy )methoxycarbonyl, (cyclohexyl)(cyclohexyloxy)methoxycarbonyl, (cyclohexyl)(phenoxy)methoxycarbonyl, (cyclohexyl)(benzyloxy)methoxycarbonyl, (Phenyl)(methoxy)methoxycarbonyl, (phenyl)(ethoxy)methoxycarbonyl, (phenyl)(n-propoxy)methoxycarbonyl, (phenyl)(isopropyl Oxy)methoxycarbonyl, (phenyl)(cyclohexyloxy)methoxycarbonyl, (phenyl)(phenoxy)methoxycarbonyl, (phenyl)(benzyloxy)methoxy Carbonyl, (benzyl)(methoxy)methoxycarbonyl, (benzyl)(ethoxy)methoxycarbonyl, (benzyl)(n-propoxy)methoxycarbonyl, (benzyl)( Isopropoxy)methoxycarbonyl, (benzyl)(cyclohexyloxy)methoxycarbonyl, (benzyl)(phenoxy)methoxycarbonyl, (benzyl)(benzyloxy)methoxycarbonyl Oxycarbonyl, etc.;

As the group represented by the above formula (B-2), for example, 2-tetrahydrofuranyloxycarbonyl, 2-tetrahydropyranyloxycarbonyl, etc.

Among them, 1-ethoxyethoxycarbonyl, 1-n-propoxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 2-tetrahydrofuranyloxycarbonyl, 2-tetrahydropyroxy pyryloxycarbonyl, etc. the

As a group containing the ketal ester structure of the said carboxylic acid, the groups respectively represented by following formula (B-3) - (B-5) are mentioned, for example. the

In formula (B-3), R ₁₅ is an alkyl group with 1 to 12 carbon atoms, R ₁₆ and R ₁₇ are each independently an alkyl group with 1 to 12 carbon atoms, and an alkyl group with 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 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 formula (B-5), R ₁₉ is an alkyl group having 1 to 12 carbon atoms, and n3 is an integer of 2 to 8.

Wherein, the _alkyl group as R in the above formula (B-3) is preferably a methyl group,

For R ₁₆ , respectively, as an alkyl group, preferably a methyl group;

As the alicyclic group, cyclohexyl is preferred;

As aryl preferably phenyl;

As aralkyl group, benzyl is preferred;

For _R17 , the alkyl group is preferably an alkyl group with 1 to 6 carbon atoms;

For alicyclic groups, preferably alicyclic groups with 6 to 10 carbon atoms;

As aryl, preferably phenyl;

As an aralkyl group, preferably benzyl or 2-phenylethyl;

The _alkyl group of R in formula (B-4) is preferably a methyl group, and n2 is preferably 3 or 4;

The alkyl group of R ₁₉ in the formula (B-5) is preferably a methyl group, and n3 is preferably 3 or 4.

Respectively, as the group represented by the above formula (B-3), for example, 1-methyl-1-methoxyethoxycarbonyl, 1-methyl-1-ethoxyethoxycarbonyl, , 1-methyl-1-n-propoxyethoxycarbonyl, 1-methyl-1-isopropoxyethoxycarbonyl, 1-methyl-1-n-butoxyethoxycarbonyl, 1 -Methyl-1-isobutoxyethoxycarbonyl, 1-methyl-1-sec-butoxyethoxycarbonyl, 1-methyl-1-tert-butoxyethoxycarbonyl, 1-methyl Base-1-cyclopentyloxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl, 1-methyl-1-norbornyloxyethoxycarbonyl, 1-methyl Base-1-bornyloxyethoxycarbonyl, 1-methyl-1-phenoxyethoxycarbonyl, 1-methyl-1-(1-naphthyloxy)ethoxycarbonyl, 1- Methyl-1-benzyloxyethoxycarbonyl, 1-methyl-1-phenethyloxyethoxycarbonyl, 1-cyclohexyl-1-methoxyethoxycarbonyl, 1-cyclohexyl -1-ethoxyethoxycarbonyl, 1-cyclohexyl-1-n-propoxyethoxycarbonyl, 1-cyclohexyl-1-isopropoxyethoxycarbonyl, 1-cyclohexyl-1- Cyclohexyloxyethoxycarbonyl, 1-cyclohexyl-1-phenoxyethoxycarbonyl, 1-cyclohexyl-1-benzyloxyethoxycarbonyl, 1-phenyl-1-methoxy Ethoxycarbonyl, 1-phenyl-1-ethoxyethoxycarbonyl, 1-phenyl-1-n-propoxyethoxycarbonyl, 1-phenyl-1-isopropoxyethoxy Carbonyl, 1-phenyl-1-cyclohexyloxyethoxycarbonyl, 1-phenyl-1-phenoxyethoxycarbonyl, 1-phenyl-1-benzyloxyethoxycarbonyl, 1 -Benzyl-1-methoxyethoxycarbonyl, 1-benzyl-1-ethoxyethoxycarbonyl, 1-benzyl-1-n-propoxyethoxycarbonyl, 1-benzyl- 1-isopropoxyethoxycarbonyl, 1-benzyl-1-cyclohexyloxyethoxycarbonyl, 1-benzyl-1-phenoxyethoxycarbonyl, 1-benzyl-1-benzyl Oxyethoxycarbonyl, etc.;

As the group represented by the above formula (B-4), for example, 2-(2-methyltetrahydrofuryl)oxycarbonyl, 2-(2-methyltetrahydropyranyl)oxycarbonyl, etc. can be mentioned;

Examples of the group represented by the formula (B-5) include 1-methoxycyclopentyloxycarbonyl, 1-methoxycyclohexyloxycarbonyl and the like. the

Among them, 1-methyl-1-methoxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl and the like are preferable. the

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

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 of 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 above formula (B-6) include 1-methylcyclopropoxycarbonyl, 1-methylcyclobutoxycarbonyl, 1-methylcyclopentyloxycarbonyl, 1- Methylcyclohexyloxycarbonyl, 1-methylcyclohexyloxycarbonyl, 1-methylcyclooctyloxycarbonyl, 1-methylcyclononyloxycarbonyl, 1-methylcyclodecanyloxycarbonyl, 1- Ethylcyclopropoxycarbonyl, 1-ethylcyclobutoxycarbonyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclohexyloxycarbonyl, 1-ethylcycloheptyloxycarbonyl, 1- Ethylcyclooctyloxycarbonyl, 1-ethylcyclonononyloxycarbonyl, 1-ethylcyclodecanyloxycarbonyl, 1-(iso)propylcyclopropoxycarbonyl, 1-(iso)propylcyclobutyl Oxycarbonyl, 1-(iso)propylcyclopentyloxycarbonyl, 1-(iso)propylcyclohexyloxycarbonyl, 1-(iso)propylcyclohexyloxycarbonyl, 1-(iso)propyl Cyclooctyloxycarbonyl, 1-(iso)propylcyclononyloxycarbonyl, 1-(iso)propylcyclodecanyloxycarbonyl, 1-(iso)butylcyclopropoxycarbonyl, 1-(iso)butylcyclobutane Oxycarbonyl, 1-(iso)butylcyclopentyloxycarbonyl, 1-(iso)butylcyclohexyloxycarbonyl, 1-(iso)butylcyclohexyloxycarbonyl, 1-(iso)butylcyclooctyloxycarbonyl, 1- (Iso)butylcyclononyloxycarbonyl, 1-(iso)butylcyclodecyloxycarbonyl, 1-(iso)pentylcyclopropoxycarbonyl, 1-(iso)pentylcyclobutoxycarbonyl, 1-(iso) ) Pentylcyclopentyloxycarbonyl, 1-(iso)pentylcyclohexyloxycarbonyl, 1-(iso)pentylcyclohexyloxycarbonyl, 1-(iso)pentylcyclohexyloxycarbonyl, 1- (Iso)pentyl cyclononyloxycarbonyl, 1-(iso)pentyl cyclodecyloxycarbonyl,

1-(iso)hexylcyclopropoxycarbonyl, 1-(iso)hexylcyclobutoxycarbonyl, 1-(iso)hexylcyclopentyloxycarbonyl, 1-(iso)hexylcyclohexyloxycarbonyl, 1- (iso)hexylcycloheptyloxycarbonyl, 1-(iso)hexylcyclooctyloxycarbonyl, 1-(iso)hexylcyclononyloxycarbonyl, 1-(iso)hexylcyclodecyloxycarbonyl, 1-(iso) ) heptylcyclopropoxycarbonyl, 1-(iso)heptylcyclobutoxycarbonyl, 1-(iso)heptylcyclopentyloxycarbonyl, 1-(iso)heptylcyclohexyloxycarbonyl, 1- (iso)heptylcycloheptyloxycarbonyl, 1-(iso)heptylcyclooctyloxycarbonyl, 1-(iso)heptylcyclononyloxycarbonyl, 1-(iso)heptylcyclodecyloxycarbonyl, 1-(iso)octylcyclopropoxycarbonyl, 1-(iso)octylcyclobutoxycarbonyl, 1-(iso)octylcyclopentyloxycarbonyl, 1-(iso)octylcyclohexyloxy Carbonyl, 1-(iso)octyl cycloheptyloxycarbonyl, 1-(iso)octyl cyclooctyloxycarbonyl, 1-(iso)octyl cyclononyloxycarbonyl, 1-(iso)octyl cyclodecyl Oxycarbonyl etc. the

The group containing the tert-butyl ester structure of the above-mentioned carboxylic acid is a tert-butoxycarbonyl group. the

As [B] the compound containing an ester structure in this invention, the compound represented by following formula (B) is preferable. the

B _n R (B)

In formula (B), B is a group shown in any one of the above formulas (B-1) to (B-5) or tert-butoxycarbonyl, n is 2 and R is a single bond, or n is 2 to An integer of 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. the

As n, 2 or 3 are preferable. the

Specific examples of R in the above formula (B) include, when n is 2, single bonds, methylene groups, alkylene groups having 2 to 12 carbon atoms, and 1,2-phenylene groups. Base, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 5-sodiumsulfo-1,3-phenylene, 5-tetrabutylphosphoniumsulfonate-1 , 3-phenylene, etc.;

When n is 3, a group represented by the following formula, a benzene-1,3,5-triyl group, etc. are mentioned. the

As the above-mentioned alkylene group, a linear one is preferable. the

The [B] ester-containing compound represented by the above formula (B) can be synthesized by a conventional method of organic chemistry, or a suitable combination of conventional methods of organic chemistry. the

For example, the group B in the above formula (B) is a compound of the group represented by the above formula (B-1) (wherein, except the case where _R is a phenyl group), preferably in the presence of a phosphoric acid catalyst, by Compound R-(COOH) _n (wherein, R and n are respectively the same as those defined in the above-mentioned formula (B)) and compound R ₁₄ -O-CH=R _13' (wherein, R ₁₄ is the same as the above-mentioned formula (B-1) The definition in is the same, and R _13' is a group obtained by removing a hydrogen atom from the first carbon of the group R ₁₃ in the above formula (B-1)) and synthesized.

The group B in the above-mentioned formula (B) is the compound of the group shown in the above-mentioned formula (B-2), preferably in the presence of p-toluenesulfonic acid catalyst, compound R-(COOH) _n (wherein R and n It is synthesized by addition of a compound represented by the same definition as in the above-mentioned formula (B), respectively) and the following formula.

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

The content of the [B] ester-containing compound in the composition for aligning organic semiconductors is determined in consideration of the required heat resistance and the like, and is not particularly limited. The amount of the alkane compound, [B] ester structure-containing compound is preferably 0.1 to 50 parts by mass, more preferably 1 to 20 parts by mass, particularly preferably 2 to 10 parts by mass. the

<[C] Component: at least one polymer selected from the group consisting of polyamic acid and polyimide>

The composition for organic semiconductor alignment preferably contains at least one polymer selected from the group consisting of polyamic acid and polyimide. By containing the polymer, the composition can improve the insulation of the obtained alignment film for an organic semiconductor. In addition, while providing thermal stability and chemical stability, the adhesiveness to the insulating layer is also good. the

Hereinafter, at least one polymer selected from the group consisting of polyamic acid and polyimide will be described in order of polyamic acid and polyimide. the

(polyamic acid)

The said polyamic acid can be obtained by making tetracarboxylic dianhydride and a diamine compound react. the

As the tetracarboxylic dianhydride that can be used in the synthesis of polyamic acid, for example, 2,3,5-tricarboxycyclopentylacetic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentadicarboxylic dianhydride, 3,5,6-Tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexa Hydrogen-5-(tetrahydro-2,5-dioxo-3-furyl)-8-methyl-naphtho[1,2-c]-furan-1,3-dione, 5-(2 , 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6 - aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides, tetracarboxylic dianhydrides represented by the following formulas (F-1) to (F-14), and alicyclic tetracarboxylic dianhydrides;

Pyromellitic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7 -Naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride , 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxybenzene Oxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy base) diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, Bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid)dianhydride, m-phenylene-bis(triphenylphthalic acid)dianhydride, Bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, the following formula (F Aromatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides represented by -15) to (F-18), respectively. the

Preferred among them are 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1, 2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-8 -Methyl-naphtho[1,2-c]-furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic dianhydride, butane tetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3' , 4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride or the tetracarboxylic dianhydride represented by said formula (F-1), (F-2), and (F-15)-(F-18), respectively. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types. the

Examples of diamine compounds that can be used to synthesize polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzoanilide, 4,4'-diaminodiphenyl ether, 4,4'-diamino-2,2'-dimethylbiphenyl, 1,5-diaminonaphthalene , 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino- 1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether, 2,2-bis(4-aminophenoxy)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis( 4-aminophenyl) hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 2,7-diamino Fluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4, 4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 4,4'-(p-phenyleneisopropylidene)bis(aniline), 4,4'-(m-phenyleneisopropylidene)bis(aniline), 2,2 -bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 6-(4-chalconyloxy)hexyloxy(2,4- Diaminobenzene), 6-(4'-fluoro-4-chalconyloxy)hexyloxy (2,4-diaminobenzene), 8-(4-chalconyloxy)octyloxy Base (2,4-diaminobenzene), 8-(4'-fluoro-4-chalconyloxy)octyloxy (2,4-diaminobenzene), 1-dodecyloxy -2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy Base-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy -2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzoyl), tetradecyloxy (3,5-diaminobenzoyl), pentadecyloxy (3,5-diaminobenzoyl), hexadecyloxy (3,5-diaminobenzoyl acyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl) Benzoyl), (2,4-diaminophenoxy)palmitate, (2,4-diaminophenoxy)stearate, (2,4-diaminophenoxy)-4 - Aromatic diamines such as trifluoromethyl benzoate and diamine compounds represented by the following formulas (G-1) to (G-5);

Aromatic diamines with heteroatoms such as diaminotetraphenylthiophene;

m-Xylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8- Octanediamine, 1,9-nonanediamine, 4,4-diamino-1,7-heptanediamine, 1,4-diaminocyclohexane, cyclohexanedi(methylamine), tetrahydroethylene Dicyclopentadiene diamine, isophorone diamine, hexahydro-4,7-methanoindenylidene (methanoindenylidene) dimethylene diamine, tricyclic [6.2.1.0 ^2,7 ] Undecyldimethyldiamine, 4,4'-methylenebis(cyclohexylamine) and other aliphatic diamines or alicyclic diamines;

Diaminoorganosiloxanes such as diaminohexamethyldisiloxane and the like. the

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, cyclohexane Alkanedi(methylamine), 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 4,4'-(p-phenylene isopropylidene ) benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4 -(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-di(trifluoromethyl)biphenyl, 4,4' -Bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy -2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecyloxy (3, 5-diaminobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3 , 5-diaminobenzoyl) or the diamines represented by the above formulas (G-1) to (G-5). These diamines can be used individually or in combination of 2 or more types. the

As the usage ratio of tetracarboxylic dianhydride and diamine compound used in the synthesis reaction of polyamic acid, the ratio of the acid anhydride group of tetracarboxylic dianhydride is preferably 0.2 to 2 equivalents with respect to the amino group contained in 1 equivalent of diamine compound. , more preferably a ratio of 0.3 to 1.2 equivalents. the

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent, preferably at -20 to 150°C, more preferably at a temperature of 0 to 100°C, preferably for 0.5 to 24 hours, more preferably for 2 to 10 hours. Among them, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Aprotic polar solvents such as methyl formamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, and hexamethylphosphoric triamide; Phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol, etc. The amount (a) of the organic solvent used is preferably 0.1 to 50% by mass, more preferably 5 to 30% by mass, of the total amount of tetracarboxylic dianhydride and diamine (b) relative to the total amount of the reaction solution (a+b) amount. the

As above, a reaction solution in which polyamic acid is dissolved can be obtained. The reaction solution can be directly used to prepare the composition for organic semiconductor orientation, or after separating the polyamic acid contained in the reaction solution, it can be used to prepare the composition for organic semiconductor orientation, or after the isolated polyamic acid is purified, use Used in the preparation of organic semiconductor alignment composition. The separation of polyamic acid can be carried out by injecting the above-mentioned reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or by distilling the solvent in the reaction solution by an evaporator under reduced pressure. In addition, the polyamic acid can also be refined by redissolving the polyamic acid in an organic solvent and then precipitating it in a poor solvent; or by repeating the step of depressurizing distillation with an evaporator one or more times. the

(Polyimide)

The said polyimide can be manufactured by dehydrating and ring-closing the amic acid structure which the polyamic acid obtained above has. At this time, all the amic acid structures can be dehydrated and ring-closed for complete imidization; or only a part of the amic acid structures can be dehydrated and ring-closed to form a partial imidate in which the amic acid structure and the imide ring structure coexist. the

The dehydration and ring closure of polyamic acid is preferably (i) by heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as required conduct. the

The reaction temperature in the method of heating polyamic acid in the above (i) is preferably 50 to 200°C, more preferably 60 to 170°C. When the reaction temperature is 50° C. or higher, the dehydration ring-closing reaction can sufficiently proceed, and when the reaction temperature is 200° C. or lower, a decrease in the molecular weight of the imidized polymer obtained can be suppressed. The reaction time in the method of heating polyamic acid becomes like this. Preferably it is 0.5-48 hours, More preferably, it is 2-20 hours. the

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyamic acid solution of (ii) above, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. As the usage-amount of a dehydrating agent, 0.01-20 mol is preferable with respect to 1 mol of polyamic-acid structural units. In addition, examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, collidine, lutidine, and triethylamine. However, it is not limited to this. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as solvents used for synthesizing polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180°C, more preferably 10 to 150°C. The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours. the

In the above-mentioned method (ii), as described above, a reaction solution containing a polyimide can be obtained. This reaction solution can be directly used to prepare the composition for organic semiconductor orientation, and can also be used to prepare the composition for organic semiconductor orientation after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution; after separating the polyimide, It is used for preparing the composition for organic semiconductor alignment; or after refining the isolated polyimide, it is used for preparing the composition for organic semiconductor alignment. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement is suitably used. Isolation and purification of a polyimide can be performed by the same operation as the above-mentioned method performed as a method of isolation and purification of a polyamic acid. the

When the organic semiconductor alignment composition of the present invention contains at least one polymer selected from the group consisting of polyamic acid and polyimide in addition to the photo-alignment polyorganosiloxane compound , with respect to 100 parts by mass of the photo-alignment polyorganosiloxane compound, the suitable ratio of both is that the total amount of polyamic acid and polyimide is 100-5,000 parts by mass, more preferably 200-2,000 parts by mass. the

(other polymers)

The above-mentioned other polymers can be used to further improve the solution properties of the organic semiconductor alignment composition of the present invention and the electrical properties of the resulting organic semiconductor alignment film. Examples of such other polymers include, for example, polyorganosiloxanes having a repeating unit having a structure different from the repeating unit represented by the above formula (3), its hydrolyzate, and a condensate of its hydrolyzate. At least one selected (hereinafter referred to as "other polyorganosiloxane"), polyamic acid ester, polyester, polyamide, cellulose derivatives, polyacetal, polystyrene derivatives, poly(benzene Ethylene-phenylmaleimide) derivatives, poly(meth)acrylates, etc. the

(Other polyorganosiloxanes)

The composition for organic semiconductor alignment of the present invention may contain other polyorganosiloxanes in addition to the photo-alignment polyorganosiloxane compound as described above. In the present invention, when other polyorganosiloxane is contained, it is preferably a group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (5), its hydrolyzate, and a condensate of its hydrolyzate At least one selected from the group. the

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

In addition, when the organic semiconductor alignment composition contains other polyorganosiloxanes, most of the other polyorganosiloxanes exist independently from the photo-alignment polyorganosiloxane compound, and the other part exists independently from the photo-alignment polyorganosiloxane compound. It exists in the form of a condensate of an oxane compound. the

The other polyorganosiloxane can be, for example, at least one silane compound selected from the group consisting of alkoxysilane compounds and halosilane compounds (hereinafter referred to as "raw material silane compound"), preferably in a suitable In an organic solvent, in the presence of water and a catalyst, it is synthesized by hydrolysis or hydrolysis and condensation. the

Examples of raw material silane compounds that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butyl Oxysilane, tetra-tert-butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyl Tri-n-butoxysilane, tri-sec-butoxysilane, tert-butoxysilane, triphenoxymethylsilane, trichlorosilane, trimethoxysilane, trimethoxysilane Ethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, Ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl Dichlorosilane; Trimethylmethoxysilane, Trimethylethoxysilane, Trimethylchlorosilane, etc. Among them, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane. the

When synthesizing other polyorganosiloxanes, examples of organic solvents that can be used arbitrarily include alcohol compounds, ketone compounds, amide compounds, ester compounds, or other aprotic compounds. These can be used individually or in combination of 2 or more types. the

Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isoamyl alcohol, and 2-methylbutanol. Alcohol, sec-pentanol, tert-amyl alcohol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, hept-3-ol, n- Octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decyl alcohol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecyl alcohol Alkanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and other monohydric alcohol compounds;

Ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4 -Heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyol compounds;

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-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol Partial ethers of polyol compounds such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc. wait. These alcohol compounds can be used alone or in combination of two or more

Examples of the ketone compound include, for example, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone , ethyl n-butyl ketone, diisobutyl ketone, methyl n-hexyl ketone, trimethyl nonanone, cyclohexanone, 2-hexanone, methyl cyclohexanone, 2,4-pentanedione, fecund Monoketone compounds such as ketone (fenchone), acetophenone, acetonylacetone, etc.;

Acetylacetone, 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 , β-diketone compounds such as 5,5-hexafluoro-2,4-heptanedione, etc. These ketone compounds may be used alone or in combination of two or more. the

Examples of the amide compound include formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, acetamide, N -Methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formyl Morpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. These amide compounds may be used alone or in combination of two or more. the

Examples of the ester compound include ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isoacetic acid Propyl ester, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethyl acetate Butyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl Diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate 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, ethylene diacetate Alcohol esters, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl malonate, diethyl oxalate, di-n-butyl oxalate, lactic acid Methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, dimethyl phthalate, diethyl phthalate, etc. These ester compounds may be used alone or in combination of two or more. the

As other aprotic compounds, for example, acetonitrile, dimethylsulfoxide, N,N,N',N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrrolidine, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiperazine, N-methyl Imidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3 -Dimethyltetrahydro-2(1H)-pyrimidinone and the like. the

Among these solvents, polyol compounds and partial ether or ester compounds of polyol compounds are particularly preferred. the

The amount of water used in the synthesis of other polyorganosiloxanes is preferably 0.01 to 100 mol, more preferably 0.1 to 30 mol, and still more preferably It is a ratio of 1 to 1.5 mol. the

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

As the above-mentioned metal chelate compound, for example, triethoxy mono(acetylacetonate) titanium, tri-n-propoxy mono(acetylacetonate) titanium, triisopropoxy mono(acetylacetonate) titanium, triisopropoxy mono( acetylacetonate) titanium, tri-n-butoxy mono(acetylacetonate) titanium, tri-sec-butoxy mono(acetylacetonate) titanium, tri-tert-butoxy mono(acetylacetonate) titanium Pyruvate) titanium, diethoxy bis(acetylacetonate) titanium, di-n-propoxy bis(acetylacetonate) titanium, diisopropoxy bis(acetylacetonate) titanium ) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-tert-butoxy bis(acetylacetonate) titanium , monoethoxy tri(acetylacetonate) titanium, mono-n-propoxy tri(acetylacetonate) titanium, mono-isopropoxy tri(acetylacetonate) titanium, mono n-butoxy·tri(acetylacetonate)titanium, mono-sec-butoxy·tri(acetylacetonate)titanium, mono-tert-butoxy·tri(acetylacetonate)titanium, tetra( acetylacetonate) titanium,

Triethoxy mono(ethyl acetoacetate) titanium, tri-n-propoxy mono(ethyl acetoacetate) titanium, triisopropoxy mono(ethyl acetoacetate) titanium, tri-n-butoxy Mono(ethyl acetoacetate) titanium, tri-sec-butoxy mono(ethyl acetoacetate) titanium, tri-tert-butoxy mono(ethyl acetoacetate) titanium, diethoxy bis(ethyl acetoacetate) ) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-secondary Butoxy bis (ethyl acetoacetate) titanium, di-tert-butoxy bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tri ( Ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) ) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl acetoacetate) titanium, bis (acetyl acetonate) Titanium chelates such as bis(ethyl acetoacetate)titanium tri(acetylacetonate)mono(ethyl acetoacetate)titanium;

Triethoxy mono(acetylacetonate) zirconium, tri-n-propoxy mono(acetylacetonate) zirconium, triisopropoxy mono(acetylacetonate) zirconium, tri-n-butyl Oxygen mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-tert-butoxy mono(acetylacetonate) zirconium, diethoxy· Bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, diisopropoxy bis(acetylacetonate) zirconium, di-n-butoxy bis( acetylacetonate) zirconium, bis-butoxy bis(acetylacetonate) zirconium, di-tert-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium mono-n-propoxy tris(acetylacetonate) zirconium, monoisopropoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium ) zirconium, mono-sec-butoxy tris(acetylacetonate) zirconium, mono-tert-butoxy tris(acetylacetonate) zirconium, tetrakis(acetylacetonate) zirconium, triethoxy· Mono(ethyl acetoacetate) zirconium, tri-n-propoxy mono(ethyl acetoacetate) zirconium, triisopropoxy mono(ethyl acetoacetate) zirconium, tri-n-butoxy mono(ethyl acetoacetate) ester) zirconium, tri-sec-butoxy mono(ethyl acetoacetate) zirconium, tri-tert-butoxy mono(ethyl acetoacetate) zirconium,

Diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium Bis(ethyl acetoacetate) zirconium, bis-butoxy di(ethyl acetoacetate) zirconium, di-tert-butoxy di(ethyl acetoacetate) zirconium, monoethoxy tri(ethyl acetoacetate) ) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, monoisopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-secondary Butoxy tris (ethyl acetoacetate) zirconium, mono-tert-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonate) tris (ethyl acetoacetate) ester) zirconium, bis(acetylacetonate) bis(ethyl acetoacetate) zirconium, tris(acetylacetonate) mono(ethyl acetoacetate) zirconium and other zirconium chelates;

Aluminum chelates such as tris(acetylacetonate)aluminum and tris(ethyl acetoacetate)aluminum, etc. the

Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, oxalic acid, maleic acid, adipic acid, methylmalonic acid, Sebacic acid, gallic acid, butyric acid, mellitic acid, arachidoleic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleadienoic 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, lemon acid, tartaric acid, etc. the

As said inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid etc. are mentioned, for example. the

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethylamine, Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, etc. the

As said alkali metal compound, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide etc. are mentioned, for example. These catalysts may be used alone or in combination of two or more. the

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

The usage-amount of a catalyst is preferably 0.001-10 mass parts with respect to 100 mass parts of raw material silane compounds, More preferably, it is 0.001-1 mass parts. the

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

The water added when synthesizing other polyorganosiloxanes may be intermittently or continuously added to the silane compound as a raw material or to a solution in which a silane compound is dissolved in an organic solvent. the

The reaction temperature at the time of synthesizing another 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. the

(Use ratio of other polymers) 

When the composition for aligning an organic semiconductor of the present invention contains other polymers and the aforementioned photo-alignment polyorganosiloxane compound, the content of the other polymer is preferably It is 10,000 mass parts or less. A more preferable content of other polymers varies depending on the type of other polymers. the

On the other hand, when the composition for aligning organic semiconductors of the present invention contains a photo-alignment polyorganosiloxane compound and other polyorganosiloxanes, the preferred proportion of both is relative to 100 parts by mass of the photo-alignment polyorganosiloxane compound. The amount of the organosiloxane compound and other polyorganosiloxanes is 100 to 2,000 parts by mass. When the composition for organic semiconductor alignment of this invention contains a photo-alignment polyorganosiloxane compound and another polymer, it is preferable that it is another polyorganosiloxane as a kind of another polymer. the

(curing agent and curing catalyst, and curing accelerator) 

The above-mentioned curing agent and curing catalyst are contained in the photo-alignment polyorganosiloxane compound for the purpose of making the crosslinking reaction of the photo-alignment polyorganosiloxane compound stronger. The above-mentioned curing accelerator is contained in the composition for organic semiconductor alignment of the present invention for the purpose of accelerating the curing reaction of the curing agent. the

As the curing agent, a curing agent commonly used for curing a curable composition containing a curable compound having an epoxy group or a compound having an epoxy group can be used. Examples of such curing agents include polyvalent amines, polyvalent carboxylic acid anhydrides, and polyvalent carboxylic acids. the

As said polyhydric carboxylic acid anhydride, the acid anhydride of cyclohexane triacid, and other polyhydric carboxylic acid anhydrides are mentioned, for example. the

Specific examples of cyclohexane tricarboxylic 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-anhydride, etc., as other polycarboxylic acid anhydrides, for example, 4-methyltetrahydrophthalic anhydride, methyl sodium Dick's anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, a compound represented by the following formula (6),

(In formula (6), p is an integer from 1 to 20.)

Tetracarboxylic dianhydride commonly used in the synthesis of polyamic acid, and Diels-Alder reaction products of alicyclic compounds with conjugated double bonds such as α-terpene and allo-ocimene and maleic anhydride and their hydrogen addition things etc. the

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

Above-mentioned curing accelerator, can enumerate such as imidazole compound;

Quaternary phosphonium compounds;

Quaternary ammonium compounds;

Diazobicycloalkenes such as 1,8-diazobicyclo[5.4.0]undecene-7 and its organic acid salts;

Organometallic compounds such as zinc octoate, tin octoate, aluminum acetylacetonate complexes;

Boron compounds like boron trifluoride, triphenyl borate;

Metal halides like zinc chloride, tin chloride;

High melting point dispersive latent curing accelerators such as dicyandiamides, amine and epoxy resin adducts such as amine addition accelerators;

Microcapsule latent curing accelerator formed by covering the surface of quaternary phosphonium salt with polymer;

Amine salt type latent curing accelerator;

Pyrolysis-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salts and Bronsted acid salts, etc. the

(epoxy compound)

The above-mentioned epoxy compound may be contained in the composition for organic semiconductor alignment of the present invention from the viewpoint of further improving the adhesiveness of the formed organic semiconductor alignment film to the surface of the insulating film. the

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-di(N,N-diglycidylaminomethyl) Cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl Glyceryl-aminomethylcyclohexane and the like are preferred compounds. the

When the composition for aligning an organic semiconductor of the present invention contains an epoxy compound, the proportion thereof is preferably 0.01 to 40 parts by mass based on a total of 100 parts by mass of the aforementioned photo-alignable polyorganosiloxane compound and other polymers optionally used. Part or less, More preferably, it is 0.1-30 mass parts. the

In addition, when the composition for organic semiconductor alignment of the present invention contains an epoxy compound, it can be used together with a basic catalyst such as 1-benzyl-2-methylimidazole for the purpose of efficiently causing the crosslinking reaction. the

(functional silane compound)

The above-mentioned functional silane compound can be used for the purpose of further improving the adhesiveness between the obtained organic semiconductor alignment film and the substrate or gate. Examples of functional silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, etc. , 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxy 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-di( Oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-glycidylpropyltrimethoxysilane, etc. In addition, the reaction product of tetracarboxylic dianhydride and silane compound having an amino group described in JP-A No. 63-291922, etc. . the

When the composition for aligning an organic semiconductor of the present invention contains a functional silane compound, its content ratio is preferably 50 parts by mass relative to the total of 100 parts by mass of the above-mentioned photo-alignment polyorganosiloxane compound and other polymers optionally used. parts or less, more preferably 20 parts by mass or less. the

(Surfactant)

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine-containing Surfactant etc. the

When the composition for aligning organic semiconductors contains a surfactant, the ratio thereof is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the composition for aligning organic semiconductors as a whole. the

(photosensitizing compound)

The photosensitizing compound that can be contained in the organic semiconductor alignment composition has a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein, R is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms) ), at least one group selected from the group consisting of -CH=CH ₂ and SO ₂ Cl, and a compound with a photosensitizing structure. The photo-alignment polyorganosiloxane compound contained in the organic semiconductor alignment composition of the present invention is also It has a photosensitive structure (cinnamic acid structure) derived from a specific cinnamic acid derivative and a photosensitizing structure derived from a photosensitizing compound. The photosensitizing structure has the function of providing a photosensitive structure close to the excitation energy in the polymer by being excited by light irradiation. This excited state may be a single state or a triple state, but a triple state is preferable in view of long lifetime and efficient transfer of energy. The light absorbed by the photosensitizing structure is preferably ultraviolet light or visible light with a wavelength in the range of 150 to 600 nm. Light having a wavelength shorter than the above lower limit cannot be applied to the photoalignment method because it cannot be handled by a normal optical system. On the other hand, light having a wavelength longer than the above-mentioned upper limit has low energy, and it is difficult to excite the excited state of the above-mentioned photosensitizing structure.

As the photosensitizing structure, for example, acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure, fluorene structure, naphthalene structure, anthracene structure, acridine structure, A pyridine structure, an indole structure, and the like can be used alone or in combination of two or more. These photosensitizing structures are obtained by removing acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene, acridine or indole, respectively. A structure formed by a group derived from 1 to 4 hydrogen atoms. Among them, the acetophenone structure, the carbazole structure, and the indole structure are each preferably a structure formed by removing 1 to 4 of the hydrogen atoms contained in the benzene ring of acetophenone, carbazole, or indole. . Among these photosensitizing structures, preferably at least one selected from the group consisting of acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure and naphthalene structure One, particularly preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure and a nitroaryl structure. the

The photosensitizing compound is preferably a compound having a carboxyl group and a photosensitizing structure, and examples of more preferable compounds include compounds represented by the following formulas (H-1) to (H-10), respectively. the

In the formula, q is an integer of 1-6. the

The photo-alignment polyorganosiloxane compound used in the present invention is obtained by combining the above-mentioned polyorganosiloxane having an epoxy group with a specific cinnamic acid derivative and a photosensitizing compound, preferably in the presence of a catalyst, Preference is given to reaction synthesis in organic solvents. In this case, the specific cinnamic acid derivative is preferably contained in an amount of 0.001 to 1 mol, more preferably 0.1 to 1 mol, and still more preferably 0.2 to 0.9 mol with respect to 1 mol of silicon atoms of polyorganosiloxane having an epoxy group. range of use. The photosensitizing compound is preferably used in an amount of 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, and still more preferably 0.001 to 0.1 mol, based on 1 mol of silicon atoms in the polyorganosiloxane having an epoxy group. the

(Preparation of composition for organic semiconductor alignment) 

The composition for aligning organic semiconductors of the present invention, as described above, contains a photo-alignment polyorganosiloxane compound as an essential component, and may contain other optional components as needed. It is preferable to dissolve each component in an organic solvent and prepare a solution. combination. In addition, the photo-alignment polyorganosiloxane compound and other components (for example, at least one polymer selected from the group consisting of polyamic acid and polyimide and other polyorganosiloxane etc.) In any state of the organic semiconductor alignment composition and the organic semiconductor alignment film, a part may be connected to each other. the

As the organic solvent that can be used to prepare the composition for organic semiconductor alignment of the present invention, a solvent that dissolves the photo-alignment polyorganosiloxane compound and other components used without reacting with them is preferable. The organic solvent that can be preferably used in the composition for organic semiconductor alignment of the present invention varies depending on the type of other polymers optionally added. the

In the organic semiconductor alignment composition of the present invention, the organic solvents exemplified above as the solvent used for synthesizing polyamic acid can be mentioned as a preferable organic solvent with respect to the photo-alignment polyorganosiloxane compound. At this time, it can also be used together with the poor solvent exemplified as the organic solvent used in the synthesis of the polyamic acid of the present invention. These organic solvents can be used individually or in combination of 2 or more types. the

On the other hand, when the organic semiconductor alignment composition of the present invention contains a photo-alignment polyorganosiloxane compound and other polyorganosiloxane as a polymer, examples of preferable organic solvents include 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, Propylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether , Ethylene Glycol Monohexyl Ether, Diethylene Glycol, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Propyl Cellosolve Acetate, Butyl Cellosolve Acetate, Methyl Carbit Alcohol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, acetic acid n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, etc. Among them, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-amyl acetate, and the like are preferable. the

The preferred solvent used in the preparation of the organic semiconductor alignment composition of the present invention can be obtained by combining one or more of the above-mentioned organic solvents according to the presence or absence of other polymers and their types. Such a solvent does not precipitate components contained in the composition for organic semiconductor alignment at the following preferred solid content concentration, and the surface tension of the composition for organic semiconductor alignment is in the range of 25 to 40 mN/m. the

The solid content concentration of the composition for organic semiconductor orientation of the present invention, that is, the ratio of the mass of all components other than the solvent in the composition for organic semiconductor orientation to the total mass of the composition for organic semiconductor orientation is selected in consideration of viscosity, volatility, etc. selection, preferably in the range of 1 to 10% by mass. The composition for organic semiconductor alignment of the present invention is applied to an insulating film, or applied to a substrate to cover the grid, forming a coating film formed of an organic semiconductor alignment film, but when the solid content concentration is 1% by mass or more, the The film thickness of the coating film is not too small, and a good organic semiconductor alignment film can be obtained. On the other hand, when the solid content concentration is 10 mass % or less, the film thickness of the coating film can be suppressed from being too large, a good organic semiconductor alignment film can be obtained, and the viscosity of the composition for organic semiconductor alignment can be prevented from increasing, and the coating properties good. The range of the particularly preferable solid content concentration differs with the method used when apply|coating the composition for organic semiconductor alignment on an insulating film or a board|substrate. For example, in the case of using the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When the printing method is used, the solid content concentration is particularly preferably in the range of 3 to 9% by mass, whereby the solution viscosity is in the range of 12 to 50 mPa·s. When the inkjet method is used, the solid content concentration is particularly preferably in the range of 1 to 5% by mass, whereby the solution viscosity is in the range of 3 to 15 mPa·s. the

The temperature at the time of preparing the composition for organic semiconductor alignment of this invention becomes like this. Preferably it is 0 degreeC - 200 degreeC, More preferably, it is 0 degreeC - 40 degreeC. the

(Organic semiconductor alignment film)

The composition for organic semiconductor alignment of the present invention is suitable for forming an alignment film or a gate insulating film that imparts anisotropy to an organic semiconductor layer by a photo-alignment method, especially for forming an alignment film or a gate insulating film used in a field-effect type organic semiconductor element. pole insulating film. the

As a method of forming an organic semiconductor alignment film, for example, forming an insulating film on a substrate for forming a gate, forming a coating film of the organic semiconductor alignment composition of the present invention on the insulating film, or forming a coating film on a substrate for forming a gate A method of forming a coating film of the organic semiconductor alignment composition of the present invention on the coating film, and then applying an orientation method such as anisotropic polarized light to the coating film to impart orientation ability to organic semiconductor molecules. the

First, the composition for organic semiconductor alignment of the present invention is applied by an appropriate coating method such as roll coating, spin coating, printing, and inkjet. Then, a coating film is formed by preheating (pre-baking) the coated surface and then firing (post-baking). The pre-baking conditions are, for example, at 40-120°C for 0.1-5 minutes, and the post-baking conditions are preferably at 120-300°C, more preferably at 150-250°C, preferably for 5-200 minutes, more preferably for 10-100 minutes . The film thickness of the coating film after the post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm. the

Next, by irradiating the above-mentioned coating film with linearly polarized light, partially polarized light, or non-polarized light, orientation energy is imparted to the organic semiconductor molecules. Here, as light, for example, ultraviolet rays including light having a wavelength of 150 nm to 800 nm and visible light rays can be used, preferably ultraviolet rays including light having a wavelength of 300 nm to 400 nm. When the light used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be combined. When irradiating unpolarized light, the irradiating direction must be an oblique direction. the

As the light source 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. Ultraviolet rays in the aforementioned preferred wavelength region can be obtained by means of using the aforementioned light source together with, for example, a filter, a diffraction grating, and the like. the

The amount of light irradiation is not particularly limited, but is preferably 1 J/m ² or more and less than 10,000 J/m ² , more preferably 10 to 3,000 J/m ² . In addition, when imparting orientation energy to organic semiconductor molecules by a photo-alignment method on a coating film formed of a conventionally known composition for aligning organic semiconductors, a light irradiation amount of 10,000 J/m ² or more is required. However, if the composition for organic semiconductor alignment of the present invention is used, good organic semiconductor molecular alignment can be imparted even if the radiation dose during the photo-alignment method is 3,000 J/m ² or less, and further 1,000 J/m ² or less. , contributing to the improvement of the productivity of organic semiconductor devices and the reduction of manufacturing costs.

The organic semiconductor alignment film thus formed results in low polarity of the photo-alignment polyorganosiloxane compound, or non-uniform distribution of photo-alignment groups near the surface of the organic semiconductor alignment film. In particular, in this organic semiconductor alignment film, groups having a cinnamic acid structure are preferably unevenly distributed from the surface to 30% of the film thickness. The group having a cinnamic acid structure that contributes to the orientation of the organic semiconductor can more effectively induce the orientation of the organic semiconductor molecules by being non-uniformly distributed in the vicinity of the surface of the alignment film on the organic semiconductor side. the

When coating the organic semiconductor alignment composition, in order to improve the adhesion between the insulating film and the coating film, a functional silane compound, titanate, etc. may be pre-coated on the insulating film. the

(Organic semiconductor device)

The organic semiconductor element of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an example of an organic semiconductor device of the present invention. The organic semiconductor element 1 includes a gate 3 formed on a substrate 2, a gate insulating film (insulating film) 4 formed to cover the gate 3, an alignment film 5 formed on the gate insulating film 4, and an alignment film 5 formed on the alignment film 5. The source electrode 6 and the drain electrode 7 are formed, and the organic semiconductor layer 8 is formed at least between the source electrode 6 and the drain electrode 7 . In the present invention, the above-mentioned organic semiconductor alignment film formed from the composition for organic semiconductor alignment is used as the alignment film 5 . The organic semiconductor alignment film of the present invention has already been described in detail, so the description is omitted here. the

While applying a voltage (source-drain voltage) between the source 6 and drain 7 of the organic semiconductor element, if the voltage applied to the gate 3 (gate voltage: Vg) is changed, the organic semiconductor layer 8 The amount of charges (carriers) in the interface with the alignment film 5 depends on the gate voltage variation, which can change the current (source-channel) flowing through the part (channel) of the organic semiconductor layer 8 between the source electrode 6 and the drain electrode 7. drain current). In this way, in the organic semiconductor element, by controlling the gate voltage Vg, the drain current Id can be controlled. the

The organic semiconductor element of the present invention will be described with reference to the drawings. FIG. 2 is a cross-sectional view schematically showing an example of the organic semiconductor device of the present invention. The organic semiconductor element 9 includes a gate electrode 11 formed on a substrate 10, an insulating film 12 formed to cover the gate electrode 11, a source electrode 13 and a drain electrode 14 formed on the gate insulating film 12, and at least the above-mentioned source electrode 13. and the organic semiconductor layer 15 formed between the drain electrode 14. In the present invention, the above-mentioned organic semiconductor alignment film formed of the composition for organic semiconductor alignment containing the component [C] is used as the gate insulating film 12 . the

When a voltage (source-drain voltage) is applied between the source 13 and the drain 14 of the organic semiconductor element, if the voltage (gate voltage: Vg) applied to the gate 11 is changed, the organic semiconductor layer 15 and the gate In the interface of the electrode insulating film 12, the amount of charges (carriers) varies depending on the gate voltage, and the current (source-drain) flowing through the part (channel) of the organic semiconductor layer 15 between the source 13 and the drain 14 between currents). In this way, in the organic semiconductor element, by controlling the gate voltage Vg, the drain current Id can be controlled. the

The π-orbital conjugation plane or π-stacking of organic semiconductor materials is closely related to the direction of carrier movement. In order to increase the mobility μ of carriers in the organic semiconductor layer, it is important not only to align the orientation of organic semiconductor molecules in one direction, but also to define π-orbital conjugated planes or π-stacking. In the organic semiconductor element of the present invention, the alignment film can be oriented by the photo-alignment method, whereby anisotropy can be imparted to the orientation of the organic semiconductor molecules, so the microscopic arrangement of the organic semiconductor molecules can define the π-orbital conjugated plane or π Stacking can also form an organic semiconductor alignment film with excellent flatness without uneven alignment. In addition, it can eliminate friction damage caused by friction, eliminate the problem of cross-contamination adhesion, and suppress off-state current. the

The insulating substrate is not particularly limited, and for example, inorganic materials such as glass and quartz, and photosensitive substrates such as acrylic, vinyl, ester, imide, urethane, diazo, and cinnamoyl can be used. Permanent polymer compounds, polyvinylidene fluoride, polyethylene terephthalate, polyethylene and other organic materials, organic-inorganic hybrid materials. In addition, two or more layers of these materials may be laminated and used, which is effective for the purpose of improving insulation withstand voltage. the

The gate insulating film formed in the organic semiconductor device of the present invention may be one layer or two or more layers. As a material for the gate insulating film 4 formed in the organic semiconductor element 1 of FIG. 1 , various known materials can be used in combination. Known materials are not particularly limited, and inorganic materials such as SiO ₂ , SiN, Al ₂ O ₃ , Ta ₂ O ₅ , polyamic acid, polyimide, polyacrylonitrile, polytetrafluoroethylene, polyethylene, etc. can be used. Organic materials such as alcohol, polyvinylphenol, polyethylene terephthalate, polyvinylidene fluoride, and organic-inorganic hybrid materials. Preferably, organic materials are preferred from the viewpoint that a low-cost liquid phase process can be utilized. Moreover, the said polyamic acid and polyimide which can be contained in this composition for organic semiconductor alignment can be used as polyamic acid and polyimide. In addition, the gate insulating film 12 formed on the organic semiconductor element 9 in FIG. 2 may be one layer or two or more layers, and at least one layer is an organic semiconductor alignment film formed by the organic semiconductor alignment composition containing [C] component. As the material of the gate insulating film forming the other layers, the same materials as those exemplified above as the material of the gate insulating film 4 formed as the organic semiconductor element 1 in FIG. 1 can be used.

The organic semiconductor molecule constituting the organic semiconductor layer of the organic semiconductor device of the present invention is not particularly limited as long as it is a conjugated compound having a conjugated double bond. For example suitable are the compounds shown below:

Polyacetylene derivatives, polythiophene derivatives with thiophene rings, poly(3-alkylthiophene) derivatives, poly(3,4-ethylenedioxythiophene) derivatives, polythiopheneacetylene derivatives, benzene Ring polyphenylene derivatives, poly(p-phenylene vinylene derivatives), polypyridine derivatives with nitrogen atoms, polypyrrole derivatives, polyaniline derivatives, polyquinoline derivatives and other conjugated polymer compounds;

Oligomers represented by dimethylhexathiophene and octathiophene;

Acenes represented by perylene, naphthacene, and pentacene;

Stacked organic molecules represented by copper phthalocyanine derivatives;

Discotic liquid crystals represented by triphenylene derivatives;

Smectic liquid crystals represented by phenylnaphthalene derivatives and benzothiazole derivatives; and

Liquid crystal polymers are represented by poly(9,9-dialkylfluorene-bithiophene) copolymers. Among them, the organic semiconductor molecule is not limited thereto. the

Among these organic semiconductor molecules, polymer compounds having the above-mentioned conjugated structures are suitable from the viewpoint that a liquid phase process can be utilized. The molecular weight of these conjugated polymer compounds is not particularly limited, but in consideration of solubility in solvents, film-forming properties, etc., the mass average molecular weight is preferably 5,000 to 500,000. the

The organic semiconductor layer used in the organic semiconductor element may contain appropriate dopants to adjust its electrical conductivity. Examples of the type of dopant include electron-accepting I ₂ , Br ₂ , Cl ₂ , ICl, BF ₃ , PF ₅ , H ₂ SO ₄ , FeCl ₃ , TCNQ (tetracyanoquinodimethane), donating Electron Li, K, Na, Eu, alkylsulfonate, alkylbenzenesulfonate, etc. as surfactant.

The gate, source, and drain used in the organic semiconductor device of the present invention are not particularly limited as long as they are conductors. As the constituent materials of each electrode, metal materials such as Al, Cu, Ti, Au, Pt, Ag, Cr, inorganic materials such as polysilicon, silicide, ITO (Indium Tin Oxide), _SnO2, etc. can be used, and heavily doped Conductive polymer materials represented by polypyridine, polyacetylene, polyaniline, polypyrrole, and polythiophene, and conductive inks in which carbon particles, silver particles, etc. are dispersed. In particular, when used in flexible electronic paper or the like, it is preferable that each electrode is a conductive ink in which a conductive polymer, carbon particles, silver particles, etc. are dispersed, since thermal expansion tends to match that of the substrate.

(Manufacturing method of organic semiconductor device)

The manufacturing method of the organic semiconductor element of the present invention comprises the step of forming an insulating film so as to cover the gate electrode formed on the substrate, the step of forming a coating film on the above-mentioned insulating film with the composition for organic semiconductor alignment, An electrode forming step of forming a source electrode and a drain electrode on the above-mentioned coating film, and an organic semiconductor layer forming step of forming an organic semiconductor layer at least between the above-mentioned source electrode and the drain electrode, and further including before the above-mentioned organic semiconductor layer forming step, A step of forming an organic semiconductor alignment film by irradiating linearly polarized light on the coating film. the

A method for producing an organic semiconductor device according to another embodiment of the present invention includes a coating film forming step of forming a coating film covering a gate electrode formed on a substrate using the composition for aligning an organic semiconductor, and forming a source electrode on the coating film. and a drain electrode forming step, and an organic semiconductor layer forming step of forming an organic semiconductor layer at least between the above-mentioned electrode and the drain electrode, and further including, before the above-mentioned organic semiconductor layer forming step, irradiating the above-mentioned coating film with linearly polarized light to form an organic semiconductor layer. The process of semiconductor alignment film. the

The method for forming the gate insulating film and the organic semiconductor layer constituting the organic semiconductor element of the present invention is not particularly limited, and can be formed by, for example, electrolytic polymerization, casting, spin coating, screen printing, dip coating, and micro-molding. (micro mold method), micro contact method, inkjet method, roller coating method, LB method, etc. In addition, the formation method of each electrode may employ a vacuum vapor deposition method, a CVD method, an electron beam vapor deposition method, a resistance heating vapor deposition method, a sputtering method, etc., depending on the material to be used. the

Alternatively, they can be patterned into desired shapes by photolithography and etching processes. In addition, soft etching and an inkjet method are also effective methods for patterning. In addition, electrodes drawn from the respective electrodes, a protective film, and the like may be formed as necessary. the

【Example】

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples. the

The mass average molecular weight (Mw) of the polyorganosiloxane having an epoxy group and the photo-alignment polyorganosiloxane compound obtained in the following examples is the polyorganosiloxane measured by gel permeation chromatography (GPC) in the following manner. Styrene converted value. the

Column: Tosoh Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40°C

Pressure: 68kgf/ ^cm2

In addition, the necessary amounts of the raw material compounds and polymers used in the following examples were secured by synthesizing the raw material compounds and polymers by repeating the synthetic routes shown in the following synthesis examples as necessary. the

<Synthesis of Polyorganosiloxane with Epoxy Group>

[Synthesis Example 1]

In a reaction vessel with a stirrer, a thermometer, a dropping funnel and a reflux condenser, add 100.0 g of 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl iso Butyl ketone and 10.0 g of triethylamine were mixed at room temperature. the

Next, after adding 100 g of deionized water dropwise over 30 minutes from the dropping funnel, it was reacted at 80° C. for 6 hours while mixing under reflux. After the reaction, the organic layer was taken out, washed with 0.2 mass % ammonium nitrate aqueous solution until the washed water was neutral, and the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane with epoxy groups, which was viscous transparent liquid. the

¹ H-NMR analysis was performed on this polyorganosiloxane having an epoxy group, and a peak based on the epoxy group with theoretical intensity was obtained near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no side effects were generated by the epoxy group during the reaction. reaction. Table 1 shows the viscosity, Mw, and epoxy equivalent of the obtained epoxy group-containing polyorganosiloxane.

[Synthesis Example 2-3]

Polyorganosiloxanes having epoxy groups were obtained as viscous transparent liquids in the same manner as in Synthesis Example 1, except that the raw materials added were as shown in Table 1. Table 1 shows the Mw and epoxy equivalent of the obtained epoxy group-containing polyorganosiloxane. the

In addition, in Table 1, the abbreviation of a raw material silane compound has the following meanings, respectively. the

ECETS: 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane

MTMS: Methyltrimethoxysilane

PTMS: Phenyltrimethoxysilane

【Table 1】

<Synthesis of specific cinnamic acid derivatives>

The synthetic reactions of specific cinnamic acid derivatives were all carried out in an inert atmosphere. the

[Synthesis Example 4]

In a 500mL three-necked flask with a condenser tube, add 20g of 4-bromodiphenyl ether, 0.18g of palladium acetate, 0.98g of tris(2-tolyl)phosphine, 32.4g of triethylamine, 135mL of dimethyl ethyl amides. Next, 7 g of the acrylic acid mixed solution was added with a syringe and stirred. The mixed solution was 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, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution, and the precipitate was recovered. The precipitate was recrystallized from 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)). the

[Synthesis Example 5]

In a 300mL three-necked flask with a condenser, mix 6.5g of 4-fluorophenylboronic acid, 10g of 4-bromocinnamic acid, 2.7g of tetrakis(triphenylphosphine)palladium, 4g of sodium carbonate, 80mL of tetrahydrofuran, 39 mL of pure water. Then, the reaction solution was heated and stirred at 80° C. for 8 hours, and it was confirmed by TLC that the reaction was complete. After the reaction solution was cooled to room temperature, 200 mL of 1N hydrochloric acid aqueous solution was poured into it, and a solid was precipitated by filtration. The obtained solid was dissolved in ethyl acetate, and washed successively with 100 mL of 1N aqueous hydrochloric acid solution, 100 mL of pure water, and 100 mL of saturated brine. 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)). the

[Synthesis Example 6]

In a 200mL three-necked flask with a condenser, mix 3.6g of 4-fluorostyrene, 6g of 4-bromocinnamic acid, 0.059g of palladium acetate, 0.32g of tris(2-tolyl)phosphine, 11g of triethyl Amine, 50 mL dimethylacetamide. The solution was heated and stirred at 120° C. for 3 hours, and after the completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. After filtering the precipitate, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution, and the precipitate was recovered. The precipitate was recrystallized from ethyl acetate to obtain 4.1 g of a compound represented by the following formula (K-3) (specific cinnamic acid derivative (K-3)). the

[Synthesis Example 7]

In a 200mL three-necked flask with a condenser tube, add 9.5g of 4-vinylbiphenyl, 10g of 4-bromocinnamic acid, 0.099g of palladium acetate, 0.54g of tris(2-tolyl)phosphine, 18g of triethyl Amine, 80 mL dimethylacetamide. The solution was heated and stirred at 120° C. for 3 hours, and after the completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. After filtering the precipitate, the filtrate was poured into 500 mL of 1N hydrochloric acid aqueous solution, and the precipitate was recovered. This precipitate was recrystallized from a 1:1 solution of dimethylacetamide and ethanol to obtain 11 g of a compound represented by the following formula (K-4) (specific cinnamic acid derivative (K-4)). the

[Synthesis Example 8]

Add 91.3g of methyl 4-hydroxybenzoate, 182.4g of potassium carbonate, and 320mL of N-methyl-2-pyrrolidone into a 1L eggplant-shaped flask, and after stirring for 1 hour at room temperature, add 99.7g of 1-bromo Pentane, stirred at 100°C for 5 hours. After the reaction was finished, it was precipitated again with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to perform a hydrolysis reaction. After the reaction was completed, it was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to obtain 102 g of white crystals of 4-pentyloxybenzoic acid. 10.41 g of the obtained 4-pentyloxybenzoic acid was taken out to a reaction vessel, 100 mL of thionyl chloride and 77 mL of N,N-dimethylformamide were added thereto, and stirred at 80° C. for 1 hour. Next, thionyl chloride was distilled off under reduced pressure, methylene chloride was added, washed with aqueous sodium bicarbonate, dried over magnesium sulfate, concentrated, and tetrahydrofuran was added to form a solution. Next, in a 500 mL three-necked flask different from the above, 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 added. The aqueous solution was ice-cooled, and the above-mentioned tetrahydrofuran solution was slowly added dropwise, followed by stirring for 2 hours to carry out a reaction. After completion of the reaction, add hydrochloric acid to neutralize, extract with ethyl acetate, dry with magnesium sulfate, concentrate, and recrystallize with ethanol to obtain 9.0 g of the compound represented by the following formula (K-5) (specific cinnamic acid derivative (K-5)) as white crystals. the

[Synthesis Example 9]

In Synthesis Example 8, 9.2 g of the following formula White crystals of the compound represented by (K-6) (specific cinnamic acid derivative (K-6)). the

<[A] Synthesis of photo-alignment polyorganosiloxane compound>

[Synthesis Example 10]

In a 100mL three-necked flask, add 9.3g of the polyorganosiloxane with epoxy groups obtained in the above synthesis example 1, 26g of methyl isobutyl ketone, 3g of the specific cinnamic acid derivatives obtained in the above synthesis example 4 (K- 1) and 0.10 g of UCAT 18X (trade name: quaternary ammonium salt manufactured by Sunapro Co., Ltd.), and stirred at 80° C. for 12 hours. After the reaction was finished, it was precipitated again with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. After the solution was washed 3 times, the solvent was distilled off to obtain 6.3 g of photo-alignment polyorganosiloxane compound (S-1). It is white powder. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-1) was 3,500. the

[Synthesis Example 11]

Except for using 3 g of the specific cinnamic acid derivative (K-2) obtained in Synthesis Example 5 instead of K-1 above, the same procedure as in Synthesis Example 10 was carried out to obtain 7.0 g of a photo-alignment polyorganosiloxane compound (S-2) of white powder. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-2) was 4,900. the

[Synthesis Example 12]

Except using 4 g of the specific cinnamic acid derivative (K-3) obtained in Synthesis Example 6 instead of the above-mentioned K-1, it was carried out in the same manner as in Synthesis Example 10 to obtain 10 g of the photo-alignment polyorganosiloxane compound (S-3). White powder. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-3) was 5,000. the

[Synthesis Example 13]

Except for using 4.1 g of the specific cinnamic acid derivative (K-4) obtained in Synthesis Example 7 instead of K-1 above, the same procedure as in Synthesis Example 10 was carried out to obtain 10 g of a photo-alignment polyorganosiloxane compound (S-4) of white powder. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-4) was 4,200. the

[Synthesis Example 14]

Except using 3 g of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 8 instead of the above-mentioned K-1, it was carried out in the same manner as in Synthesis Example 10 to obtain 10 g of the photo-alignment polyorganosiloxane compound (S-5). White powder. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-5) was 4,200. the

[Synthesis Example 15]

In a 200mL three-necked flask, add the specific cinnamic acid derivative (K -6) (corresponding to 50 mol% with respect to the silicon atoms of the polyorganosiloxane having an epoxy group), 1.08 g of a compound represented by the following formula as a photosensitizing compound (relative to The silicon atom which the polyorganosiloxane of the base has, corresponds to 20 mol%) and 0.10 g of tetrabutylammonium bromide, and stirred at 80 degreeC for 12 hours, and reacted. After the reaction was finished, precipitate again with methanol, and dissolve the precipitate in ethyl acetate to obtain a solution. After washing the solution three times with water, the solvent was distilled off to obtain 2.8 g of a photo-alignment polyorganosiloxane compound (S-6). , as white powder. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-6) was 12,500. the

[Synthesis Example 16]

Except having used 5 g of lauric acid, it carried out similarly to synthesis example 10. As a result, 11 g of white powder of a photo-alignment polyorganosiloxane compound (S-7) was obtained. The mass average molecular weight Mw of the photo-alignment polyorganosiloxane compound (S-7) was 6,000. the

<[B] Synthesis of Compounds Containing Ester Structure>

According to the following scheme, the compound (B-1-1) containing ester structure was synthesized. the

[Synthesis Example 17]

21 g of trimesic acid, 60 g of n-butyl vinyl ether, and 0.09 g of phosphoric acid were added to a 500 mL three-neck flask equipped with a reflux tube, a thermometer, and a nitrogen gas inlet tube, and the mixture was stirred at 50° C. for 30 hours to perform a reaction. After completion of the reaction, 500 mL of hexane was added to the reaction mixture, and the obtained organic layer was sequentially washed twice with a 1M aqueous sodium hydroxide solution and three times with aqueous solution. Thereafter, the solvent was distilled off from the organic layer to obtain 50 g of an ester structure-containing compound (B-1-1) as a colorless transparent liquid. the

<Synthesis of Polyamic Acid>

[Synthesis Example 18]

Dissolve 19.61g (0.1mol) of cyclobutanetetracarboxylic dianhydride and 21.23g (0.1mol) of 4,4'-diamino-2,2'-dimethylbiphenyl into 367.6g of N-methyl- In 2-pyrrolidone, react at room temperature for 6 hours. Next, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-1). the

[Synthesis Example 19]

22.4g (0.1mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 14.23g (0.1mol) of cyclohexane di(methylamine) were dissolved into 329.3g of N-methyl-2- In pyrrolidone, the reaction was carried out at 60° C. for 6 hours. Next, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol, and dried at 40° C. for 15 hours under reduced pressure to obtain 32 g of polyamic acid (PA-2). the

[Synthesis Example 20]

As tetracarboxylic dianhydride 109g (0.50mol) of pyromellitic dianhydride and 98g (0.50mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and as diamine compound 200g (1.0mol) of 4,4'-diaminodiphenyl ether was dissolved in 2,290g of N-methyl-2-pyrrolidone, reacted at 40°C for 3 hours, and 1,350g of N-methyl-2 -Pyrrolidone, about 3,590 g of solutions containing 10% by mass of polyamic acid (PA-3) were obtained (the amount of polyamic acid is 359 g in terms of mass). the

[Synthesis Example 21]

The following formula (RA-2 The compounds shown in -1-1) were reacted to obtain polyamic acid (RPA-1). the

<Synthesis of polyimide>

[Synthesis Example 22]

17.5 g of PA-2 obtained in Synthesis Example 17 above was taken out, 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine, and 4.9 g of acetic anhydride were added thereto, and reacted at 120° C. for 4 hours to imidize. Next, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol, and dried under reduced pressure for 15 hours to obtain 15 g of polyimide (PI-1). the

<Preparation of composition for organic semiconductor alignment>

[Example 1]

100 parts by mass of the photo-alignment polyorganosiloxane compound (S-1 ) to form a solution with a solid content concentration of 4.0% by mass. This solution was filtered through a filter having a pore diameter of 1 μm to prepare a composition (A-1) for organic semiconductor alignment. the

[Example 2-5]

Various organic semiconductor alignment compositions (A-2) to (A-5) were prepared in the same manner as in Example 1 by changing the photo-alignment polyorganosiloxane compound. In addition, in Example 4, 5 parts by mass of the ester-containing compound (B-1-1) obtained in Synthesis Example 17 was added to 100 parts by mass of the photo-alignment polyorganosiloxane compound to prepare an organic semiconductor alignment compound (B-1-1). with composition. Their compounding ratio is shown in Table 2. the

[Comparative example 1]

13.1 g of poly(2-hydroxyethyl methacrylate) was heated and dissolved in 50 mL of N-methyl-2-pyrrolidone, and after cooling to room temperature, 10 mL of pyridine was added. Cinnamoyl chloride 17.0g was added there, and it stirred for 8 hours. After diluting the reaction mixture with N-methyl-2-pyrrolidone, it was added to methanol, and the precipitate was fully washed with water and dried to obtain 25 g of a polymer. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to form 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. This solution was filtered through a filter with a pore size of 1 μm to prepare a composition (CA-1). the

[Comparative example 2]

Add 1.00 g of 4-(2-methacryloyloxyethoxy) azobenzene and 0.01 g of 2,2'-azobis(isobutyronitrile) and 2.00 g of dry benzene into the ampoule, drain After degassing, the tube was sealed and injected into methanol to obtain a precipitate of a polymer compound. After filtering this, the precipitate was dissolved in benzene again, and the operation of reprecipitating with methanol and filtering was repeated twice, followed by drying. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to form 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. This solution was filtered through a filter having a pore size of 1 μm to prepare a composition (CA-2). the

<Formation of organic semiconductor alignment film and manufacture of organic semiconductor device>

A gate electrode having a thickness of 20 nm was formed on a glass substrate by a vacuum evaporation method using Al as an electrode material. Thereafter, the polyamic acid (PA-1) prepared in Synthesis Example 18 was applied by spin coating, and heated (baked) at 200° C. for 1 hour in an internal nitrogen-substituted oven to form an insulating film with a film thickness of 0.2 μm. Next, the organic semiconductor alignment composition (A-1) prepared in Example 1 was coated by a spin coater on the insulating film, prebaked on a hot plate at 80° C. for 1 minute, and then heated in an oven replaced with nitrogen inside. , heated at 200° C. for 1 hour (post-baking), to form a coating film with a film thickness of 0.1 μm. In order to make the film thickness after formation into 0.1 micrometer, the rotation speed of the spin coater was made into 2000 rpm, and the solid content concentration of the composition (A-1) for organic semiconductor alignment was 4.0 mass %. Next, the surface of the coating film was irradiated with linearly polarized ultraviolet rays including a bright line of 313 nm perpendicularly from the normal line of the substrate using a Hg-Xe lamp and a Glan-Taylor prism to form an organic semiconductor alignment film. The amount of light irradiation necessary for the orientation of the photo-alignment groups in the coating film formed at this time was measured and used as a sensitivity index of photo-orientation. In addition, the orientation of the photo-alignment group was confirmed using a polarizing microscope. the

Next, in the above-mentioned organic semiconductor alignment film, a source electrode and a drain electrode were formed by vapor deposition of gold so that the channel length was 30 μm and the channel width was 50 μm. Next, in order to cover the above two electrodes, a film thickness of modified pentacene is formed by vapor deposition. The organic semiconductor molecular film is used to manufacture top gate type organic semiconductor devices.

Organic semiconductor elements were produced in the same manner for the compositions prepared in Examples 2 to 5 and Comparative Examples 1 to 2. These organic semiconductor elements were evaluated by the following methods. The evaluation results are shown in Table 2. the

<Evaluation of Organic Semiconductor Devices>

(1) Evaluation of initial carrier mobility

The initial carrier mobility was measured for the front-gate organic semiconductor element manufactured in the above steps using a semiconductor parameter analyzer (Semiconductor parameter analyzer HP4155a, manufactured by Hiretsuto Parkcard Co., Ltd.). the

(2) Evaluation of carrier mobility after heating

This organic semiconductor element was placed under heating conditions, and the degree of carrier mobility after heating was measured to evaluate the stability against heat. Specifically, the front-gate organic semiconductor element manufactured in the above steps was heated in an oven set at 70° C. for 500 hours, and then, the same steps as in the above-mentioned “(1) Evaluation of initial carrier mobility” were carried out. Carrier mobility after heating was measured. The evaluation results are shown in Table 2. The retention rate of carrier mobility after heating is also shown in Table 2 together. the

The results in Table 2 show that, for the organic semiconductor alignment compositions of Examples 1 to 5, when using them to manufacture an organic semiconductor alignment film, the amount of light irradiation necessary for photo-alignment is extremely low, and the sensitivity of photo-alignment is good. In addition, the organic semiconductor element having the alignment film can realize high carrier mobility. In addition, even after the organic semiconductor element is heated, it can maintain the initial carrier mobility at a high rate, thereby obtaining excellent heat resistance. On the other hand, the alignment film manufactured using the composition of Comparative Example 1 had good photo-alignment sensitivity and carrier mobility of the semiconductor element, but the carrier mobility after heating was about half of the value, indicating that the resistance Poor heat. As a result of the alignment film manufactured using the composition of Comparative Example 2, a light irradiation amount of 20,000 J/m ² for photo-alignment was also required, and the carrier mobility was also lower than that of the organic semiconductor element of the embodiment. half the value.

<Preparation of an insulating organic semiconductor alignment composition>

[Example 6]

Select the above-mentioned Synthesis Example 17 to obtain a solution containing polyamic acid (PA-1), and convert the polyamic acid (PA-1) contained therein into an amount equivalent to 1,000 parts by mass, and add 100 parts by mass of the polyamic acid obtained in the above-mentioned Synthesis Example 10 to it. Photo-alignment polyorganosiloxane compound (S-1), then add N-methyl-2-pyrrolidone and butyl cellosolve to form a solvent composition N-methyl-2-pyrrolidone: butyl cellosolve=50:50 ( mass ratio) and a solid content concentration of 3.0% by mass solution. This solution was filtered through a filter having a pore diameter of 1 μm to prepare a composition for aligning an organic semiconductor (A-6). the

[Embodiment 7-14]

Various compositions (A-7) to (A-14) for organic semiconductor alignment were prepared by changing the combination of the photo-alignment polyorganosiloxane compound, polyamic acid, and polyimide. They are shown in Table 2. In addition, 50 parts by mass of the photo-alignment polyorganosiloxane compounds (S-1) and (S-7) in Example 7 were added respectively. In Example 14, the polyamic acid-containing The solution of (PA-3) is equivalent to 2,000 parts by mass in terms of polyamic acid (PA-3). the

[Comparative example 3]

A composition (CA-3) was prepared in the same manner as in Example 6 except that the photo-alignment polyorganosiloxane compound was not added. the

[Comparative example 4]

A composition (CA-4) was prepared in the same manner as in Example 6 except that the polyamic acid (PA-2) obtained in Synthesis Example 19 was used as the polyamic acid without adding the photo-alignment polyorganosiloxane compound. the

[Comparative Example 5]

A composition (CA-5) was prepared in the same manner as in Example 6 except that the polyamic acid (RPA-1) obtained in Synthesis Example 21 was used as the polyamic acid without adding the photo-alignment polyorganosiloxane compound. the

[Comparative Example 6]

13.1 g of poly(2-hydroxyethyl methacrylate) was heated and dissolved in 50 mL of N-methyl-2-pyrrolidone, and after cooling to room temperature, 10 mL of pyridine was added. Cinnamoyl chloride 17.0g was added there, and it stirred for 8 hours. After diluting the reaction mixture with N-methyl-2-pyrrolidone, it was added to methanol, and the precipitate was fully washed with water and dried to obtain 25 g of a polymer. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to form a solution having a solvent composition of N-methyl-2-pyrrolidone:butyl cellosolve=50:50 (mass ratio) and a solid content concentration of 3.0% by mass. This solution was filtered through a filter with a pore size of 1 µm to prepare a composition (CA-6). the

<Formation of insulating organic semiconductor oriented film and production of organic semiconductor device>

A gate electrode having a thickness of 20 nm was formed on a glass substrate by a vacuum evaporation method using Al. Then, the organic semiconductor orientation composition (A-6) prepared in Example 6 was coated by a spin coater, prebaked by a hot plate at 80° C. for 1 minute, and then heated at 200° C. in an internal nitrogen-substituted oven. After 1 hour (post-baking), a coating film with a film thickness of 0.2 μm was formed. In order to form a film having a thickness of 0.2 μm, the rotational speed of the spin coater was 2000 rotations, and the solid content concentration of the solvent for the alignment film was 4%. Next, the surface of the coating film was irradiated with 1,000 J/m ² of linearly polarized ultraviolet rays including a bright line of 13 nm perpendicularly from the substrate normal using a Hg-Xe lamp and a Glan-Taylor prism to form an organic semiconductor alignment film.

Next, a source electrode and a drain electrode were formed in the organic semiconductor alignment film by vapor deposition of gold so that the channel length was 30 μm and the channel width was 50 μm. Next, in order to cover the above two electrodes, a film thickness of modified pentacene is formed by vapor deposition The organic semiconductor molecular film is used to manufacture front-gate organic semiconductor devices.

Organic semiconductor devices were produced in the same manner for the compositions prepared in Examples 7 to 14 and Comparative Examples 3 to 6. These organic semiconductor elements were evaluated by the following methods. The evaluation results are shown in Table 3. the

<Evaluation of Organic Semiconductor Devices>

(1) Evaluation of volume intrinsic resistance (insulation)

Using a silicon wafer as a substrate, the organic semiconductor alignment composition (A-6) was coated with a spin coater, prebaked on a hot plate at 80° C. for 1 minute, and then heated at 200° C. for 1 minute in an oven replaced with nitrogen. hours (pre-baking), a coating film with a film thickness of 0.2 μm is formed. In order to make the formed film thickness 0.2 μm, the rotation speed of the spin coater was 2000 rotations, and the concentration of solvent and solid content of the alignment film was 4%. Next, a Hg-Xe lamp and a Glan-Taylor prism were used to irradiate the surface of the coating film with 1,000 J/m ² of linearly polarized ultraviolet rays including a bright line of 13 nm vertically from the substrate normal to form an organic semiconductor alignment film. On the surface of the alignment film, Al was vapor-deposited as an upper electrode to form a substrate for measuring the film volume specific resistance. On the same measurement substrate, a silicon wafer was used as a lower electrode and an Al electrode was used as an upper electrode. A voltage of 1 V was applied, and the current was measured with an electrometer (R12706A manufactured by Advantest Co., Ltd.) to calculate the resistivity.

(2) Evaluation of carrier mobility

Carrier mobility was measured for the front-gate type organic semiconductor element manufactured in the above steps using a semiconductor parameter analyzer (Semiconductor parameter analyzer HP4155a, manufactured by Hiretsuto Parkcard Co., Ltd.). the

【table 3】

The results shown in Table 3 show that the organic semiconductor alignment film manufactured using the organic semiconductor alignment composition of Examples 6 to 14 has excellent insulation properties, and the organic semiconductor element with the alignment film can achieve extremely high carrier mobility. . On the other hand, although the insulating films manufactured using the compositions of Comparative Examples 3 and 4 had high insulating properties, since there were no photo-alignment groups in the insulating film molecules, the carrier mobility of the semiconductor element decreased to ten times that of the examples. one-third. The semiconductor element having the insulating film produced using the composition of Comparative Example 5 had a structure derived from a diamine having photo-orientation property, or obtained a high degree of carrier mobility, but its insulating properties were low. The insulating film produced using the composition of Comparative Example 6 having no polyorganosiloxane skeleton had a resistivity lower than one digit or more, and the insulating property was poor. the

<Evaluation of Existence Distribution of Specific Cinnamic Acid Derivatives in Organic Semiconductor Alignment Film>

On the transparent electrode surface of the glass substrate with the transparent electrode formed by the ITO film, the organic semiconductor alignment composition (A-14) prepared in the above-mentioned embodiment 14 is coated by a spin coater, and placed on a hot plate at 80° C. After prebaking for 1 minute, it was heated at 210° C. for 20 minutes in an oven purged with nitrogen to form a coating film with a film thickness of 80 nm. the

Using the TOF-SIMS measurement device manufactured by ULVAC-PHI, using Bi ₃ ⁺⁺ cluster ions at an accelerating voltage of 25kV as the primary ion source, passing an ion current of 0.05pA, a measurement field of view of 100μm, and a measurement mass range of 0 to 1,850amu, On the surface of the coating film formed above, C ₆₀ sputtering and TOF-SIMS analysis were repeated until indium ions from ITO were detected, and the thickness of the coating from the surface of the coating film to a depth of 80 nm was studied at the time when indium ions were detected. Composition distribution in the film thickness direction. Figures showing the distribution of fragments at m/z=231 at this time are shown in FIG. 3 (existence distribution) and FIG. 4 (cumulative value). In addition, the graphs shown in these figures are values normalized by dividing the number of calculations of the segment at each depth by the noise level.

It is considered that the above-mentioned fragment with m/z=231 corresponds to the fragment represented by the following formula derived from the lauric acid derivative (K-6). Therefore, from the results of FIG. 3, it can be inferred that in the coating film formed in this example, groups derived from the specific cinnamic acid derivative exist on the surface of the coating film at the highest concentration, and are unevenly distributed from the surface to the thickness. 20% in this range (at most in the 30% range). the

Industrial applicability

The organic semiconductor alignment composition of the present invention contains a photo-alignment polyorganosiloxane compound, so as described above, the photo-alignment sensitivity is good, and the stability of carrier mobility after heating is excellent. The organic semiconductor element of the alignment film can induce high-level anisotropic orientation of organic semiconductor molecules through the photo-alignment groups on the surface of the organic semiconductor alignment film, thereby achieving excellent carrier mobility. the

In addition, when the organic semiconductor alignment composition of the present invention containing a photo-alignment polyorganosiloxane compound and polyamic acid and/or polyimide is used, the obtained organic semiconductor alignment film has high Insulation, so it is suitable for use in organic semiconductor devices and the like. the

Claims (11)

1. A composition for organic semiconductor alignment, which is used to form an insulating alignment film that aligns organic semiconductor molecules in different directions, the composition comprising [A] a polyorganosilicon having a photo-alignment group on a side chain An oxane compound and [C] at least one polymer selected from the group consisting of polyamic acid and polyimide, wherein the above-mentioned photo-alignment group is a group having a cinnamic acid structure, and the above-mentioned group having a cinnamic acid The group of the structure is at least one selected from the group consisting of a group from a compound shown in the following formula (1) and a group from a compound shown in (2); In formula (1), R ₁ phenylene, biphenylene, terphenylene or cyclohexylene, a part of the hydrogen atom of the phenylene, biphenylene, terphenylene or cyclohexylene or All may be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms that may have a fluorine atom as a substituent, a fluorine atom or a cyano group, _R2 is a single bond, and the number of carbon atoms is is an alkylene group 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, _R1 and _R2 can be The same or different, R ₃ is a fluorine atom or a cyano group, b is an integer of 0 to 4, In formula (2), R ₄ is phenylene or cyclohexylene, and a part or all of the hydrogen atoms of the phenylene or cyclohexylene can be replaced by a chain or cyclic alkyl group with 1 to 10 carbon atoms. , a chain or cyclic alkoxy group with 1 to 10 carbon atoms, a fluorine atom or a cyano group, _R5 is a single bond, an alkylene group with 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-, c is an integer of 1 to 3, 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, d is an integer of 0 to 4, R ₇ is an oxygen atom, -COO-* or -OCO-*, wherein, in the above, the connecting bond with "*" is connected to R ₈ , and R ₈ is a divalent aromatic group, a divalent alicyclic group, A divalent heterocyclic group or a divalent condensed ring group, R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -*, wherein, in the above, with The connection bond of "*" is connected with the carboxyl group, f and g are respectively an integer of 1-10, and e is an integer of 0-3. 2. The organic semiconductor alignment composition according to claim 1, wherein [A] the polyorganosiloxane compound having a photo-alignment group is selected from polyorganosiloxane having an epoxy group, its hydrolyzate Reaction of at least one selected from the group consisting of a condensate of its hydrolyzate and at least one selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2) product. 3. The organic semiconductor alignment composition according to claim 2, wherein the epoxy group is 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, and i is an integer of 0 to 6, wherein, when i is 0, A is a single bond, In the formula (X ₁ -2), j is an integer of 1 to 6, In the formulas (X ₁ -1) and (X ₁ -2), "*" respectively represent a connecting bond. 4. The organic semiconductor alignment composition according to any one of claims 1 to 3, further comprising [B] having two or more carboxylic acid acetal ester structures, carboxylic acid ketal ester structures, carboxylic acid A compound of at least one structure selected from the group consisting of a 1-alkylcycloalkyl ester structure and a tert-butyl ester structure of a carboxylic acid. 5. The organic semiconductor alignment composition according to claim 1, wherein said polyamic acid and polyimide are selected from the group consisting of aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride The reaction product of at least one tetracarboxylic dianhydride and at least one diamine selected from the group consisting of alicyclic diamine and aromatic diamine. 6. An organic semiconductor alignment film formed from the composition for organic semiconductor alignment according to any one of claims 1 to 5. 7. An organic semiconductor alignment film, wherein the group with the cinnamic acid structure is unevenly distributed in the range of 30% from the surface to the film thickness, wherein the above-mentioned group with the cinnamic acid structure is derived from the following formula ( 1) At least one selected from the group consisting of the group of the compound shown in (2) and the group of the compound shown in (2); In formula (1), R ₁ phenylene, biphenylene, terphenylene or cyclohexylene, a part of the hydrogen atom of the phenylene, biphenylene, terphenylene or cyclohexylene or All may be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms that may have a fluorine atom as a substituent, a fluorine atom or a cyano group, _R2 is a single bond, and the number of carbon atoms is is an alkylene group 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, _R1 and _R2 can be The same or different, R ₃ is a fluorine atom or a cyano group, b is an integer of 0 to 4, In formula (2), R ₄ is phenylene or cyclohexylene, and a part or all of the hydrogen atoms of the phenylene or cyclohexylene can be replaced by a chain or cyclic alkyl group with 1 to 10 carbon atoms. , a chain or cyclic alkoxy group with 1 to 10 carbon atoms, a fluorine atom or a cyano group, _R5 is a single bond, an alkylene group with 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-, c is an integer of 1 to 3, 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, d is an integer of 0 to 4, R ₇ is an oxygen atom, -COO-* or -OCO-*, wherein, in the above, the connecting bond with "*" is connected to R ₈ , and R ₈ is a divalent aromatic group, a divalent alicyclic group, A divalent heterocyclic group or a divalent condensed ring group, R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -*, wherein, in the above, with The connection bond of "*" is connected with the carboxyl group, f and g are respectively an integer of 1-10, and e is an integer of 0-3. 8. An organic semiconductor element comprising: gate formed on the substrate, An insulating film is formed covering the above-mentioned gate, The organic semiconductor alignment film formed on the above-mentioned insulating film by the organic semiconductor alignment composition described in any one of claims 1 to 5, The source electrode and the drain electrode formed on the above-mentioned organic semiconductor alignment film, and an organic semiconductor layer formed at least between the source and the drain. 9. A method of manufacturing an organic semiconductor element, the method comprising: An insulating film forming process of forming an insulating film to cover a gate electrode formed on the substrate; On the above-mentioned insulating film, a coating film forming process of forming a coating film by the organic semiconductor alignment composition described in any one of claims 1 to 5; An electrode formation process of forming a source electrode and a drain electrode on the above-mentioned coating film; and an organic semiconductor layer forming step of forming an organic semiconductor layer at least between the source electrode and the drain electrode; Before the said organic semiconductor layer formation process, you may further have the process of irradiating linearly polarized light to the said coating film, and forming an organic semiconductor alignment film. 10. An organic semiconductor element comprising: gate formed on the substrate, The organic semiconductor alignment film for covering the above-mentioned grid formed by the organic semiconductor alignment composition described in claim 1 or 5, The source electrode and the drain electrode formed on the above-mentioned organic semiconductor alignment film, and an organic semiconductor layer formed at least between the source and the drain. 11. A method of manufacturing an organic semiconductor element, the method comprising: A coating film forming process of forming a coating film to cover the gate formed on the substrate by the organic semiconductor alignment composition described in claim 1 or 5; An electrode formation process of forming a source electrode and a drain electrode on the above-mentioned coating film; and an organic semiconductor layer forming step of forming an organic semiconductor layer at least between the source electrode and the drain electrode; Before the step of forming the organic semiconductor layer, a step of irradiating the coating film with linearly polarized light to form an organic semiconductor alignment film may be further included.