JP5564951B2 - Composition for aligning organic semiconductor, organic semiconductor alignment film, organic semiconductor element and manufacturing method thereof - Google Patents

Description

  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 thereby, an organic semiconductor element having the organic semiconductor alignment film, and a method for producing the same About.

  In recent years, liquid crystal display elements have advantages such as low power consumption and easy miniaturization or flattening. Therefore, liquid crystal display elements can be used for small screens such as mobile phones and large screens such as liquid crystal televisions. It is applied to a wide range of applications up to liquid crystal display devices. In such a liquid crystal display element, an image is displayed by switching the liquid crystal assigned to each dot to an ON / OFF state, and a thin film transistor (TFT) is used to switch the liquid crystal ON / OFF. Yes.

  As semiconductor devices typified by field effect TFTs, inorganic semiconductors using silicon or the like are widely used, and organic semiconductors are also being developed. Organic semiconductors include low-molecular organic semiconductors and high-molecular organic semiconductors. As materials for these, pentacene has been widely studied for low-molecular organic semiconductors, and polythiophene derivatives have been widely studied for high-molecular organic semiconductors. In a low molecular weight organic semiconductor, a semiconductor layer is formed by a vapor deposition method, whereas in a high molecular weight organic semiconductor, a semiconductor layer can be formed by a coating method (spin casting, ink jet method, printing method, etc.), and vacuum -Since a coating process at room temperature in the atmosphere is possible without using a high temperature process, there is an advantage that it can be manufactured at low cost. Further, since it can be formed on a resin substrate, it is expected to be applied to various fields such as a flexible display, electronic paper, a plastic IC card, an organic EL, and a solar cell in addition to TFT.

In order to increase the functionality of an organic semiconductor, for example, in a switching TFT, a high operating frequency (for example, about several hundred kHz) and a high ON current / OFF current ratio (ON / OFF ratio. For example, about 10 ⁴ to 10 ⁶ . ) Is required. Control of the drain current between the source electrode and the drain electrode is effective for the expression of such a function. Here, with respect to the drain current (Id) in the saturation region, the following relational expression (I) is established.

Id = (W / 2L) μCi (Vg−Vt) ² (I)

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

  Therefore, W / 2L and Ci need only be increased in order to satisfy the above requirements. However, if the former W / 2L is increased, it is necessary to increase the precision of electrode pattern formation and cause an increase in cost. . On the other hand, when the latter Ci is increased, it is necessary to increase the dielectric constant of the gate insulating film and reduce the film thickness, but there are significant restrictions from the viewpoint of preventing defects such as pinholes in a large area process. Therefore, a technique focusing on the improvement of carrier mobility μ with less restrictions is being developed. As a specific method for improving carrier mobility μ, an alignment film that regulates the orientation of organic semiconductor molecules is introduced, and π orbits (π electrons) that contribute to electrical conduction by orienting organic semiconductor molecules in a predetermined direction are overlapped. Attempts have been made to increase carrier mobility and improve carrier mobility.

  The relationship between the overlap of π orbitals due to the orientation of organic semiconductor molecules and the carrier movement is considered as follows. In the π-electron conjugated polymer composing the polymer organic semiconductor, the organic semiconductor polymer chain is aligned in the same direction (inter-electrode direction) as the alignment direction of the alignment film, and as a result, carriers in the alignment direction of the main chain It can be moved. Further, in a low molecular organic semiconductor, a π stack of organic semiconductor molecules is formed in a direction perpendicular to the alignment direction of the alignment film (direction between the electrodes), so that carrier movement in the direction of overlapping π orbits is possible.

  Although there is a method to increase the anisotropy by rubbing the organic semiconductor layer in the carrier movement direction for the orientation of the organic semiconductor molecules, it does not reach the regulation of the overlap of the π orbital plane, and the occurrence of rubbing scratches and contamination There is also a risk. In order to solve such problems of the rubbing method, a non-contact type photo-alignment method has been developed. As an organic transistor adopting this photo-alignment method, for example, in Japanese Patent Application Laid-Open No. 2009-289833, an organic material including a substrate, a gate electrode, a gate insulating layer, an alignment layer, a source electrode and a drain electrode, and a specific material is used in Examples. An organic field effect transistor in which semiconductor layers are sequentially formed has been proposed.

  However, in the organic transistor of the above document, although a certain degree of carrier mobility is obtained, a considerable amount of light irradiation is required for the alignment of the photoalignable group, and it cannot be said that the photoalignment sensitivity is sufficiently high. Further, in order to apply organic semiconductors to various fields, it is necessary to have weather resistance (heat resistance) that can maintain the initial carrier mobility at a high rate even under severe usage conditions such as high temperatures. However, the above document does not take into consideration the heat resistance (carrier mobility stability) required as an alignment layer in an organic semiconductor element.

  In view of this situation, the sensitivity of photo-alignment is good, the carrier mobility is stable due to high heat resistance, and high carrier mobility is achieved by inducing anisotropic orientation of organic semiconductor molecules at a high level. Development of a possible organic semiconductor alignment film and an organic semiconductor alignment composition capable of forming the same is desired.

JP 2009-28983A

  The present invention has been made based on the circumstances as described above. The purpose of the present invention is to achieve a high level of organic semiconductor molecules while achieving good photo-alignment sensitivity and carrier mobility stability due to high heat resistance. Organic semiconductor alignment film capable of exhibiting excellent carrier mobility by anisotropic alignment, composition for organic semiconductor alignment capable of forming the same, organic semiconductor element including the organic semiconductor alignment film, and organic semiconductor element It is to provide a manufacturing method.

The invention made to solve the above problems is
[A] An organic semiconductor alignment composition containing a polyorganosiloxane compound having a photoalignment group.

  Since the composition for organic semiconductor alignment contains a polyorganosiloxane compound having a photo-alignable group [A], when forming an organic semiconductor alignment film using this, the photo-alignment is performed with good photo-alignment sensitivity. The amount of light irradiation required for the orientation of the functional group can be reduced, and thereby the production efficiency of the organic semiconductor element can be increased. In addition, a polyorganosiloxane compound having an [A] photo-alignment group anisotropically oriented in the organic semiconductor alignment film formed using the composition for organic semiconductor alignment can be used to differentiate organic semiconductor molecules at a high level. It is possible to achieve isotropic orientation, thereby achieving excellent carrier mobility in the organic semiconductor element. In addition, since the polyorganosiloxane compound having a photoalignable group [A] of the composition for organic semiconductor alignment employs polyorganosiloxane as the main chain, the thermal stability and chemistry of the resulting alignment film High stability and high heat resistance, so that the initial carrier mobility can be maintained at a high rate for a long time even after heat load.

  In the organic semiconductor alignment composition, the photo-alignment group is preferably a group having a cinnamic acid structure. By using a group having a cinnamic acid structure having cinnamic acid or a derivative thereof as a basic skeleton as a photo-alignable group, high anisotropy is imparted to the alignment of organic semiconductor molecules resulting from the obtained organic semiconductor alignment film. The carrier mobility in the organic semiconductor can be further improved.

（式（１）中、Ｒ_１は、フェニレン基、ビフェニレン基、ターフェニレン基又はシクロヘキシレン基であり、このフェニレン、ビフェニレン基、ターフェニレン基又はシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０のアルキル基、置換基としてフッ素原子を有していてもよい炭素数１〜１０のアルコキシ基、フッ素原子又はシアノ基で置換されてもよい。Ｒ_２は、単結合、炭素数１〜３のアルキレン基、酸素原子、硫黄原子、−ＣＨ＝ＣＨ−、−ＮＨ−又は−ＣＯＯ−である。ａは、０〜３の整数であり、ａが２以上の場合、Ｒ_１及びＲ_２はそれぞれ同じでも異なっていてもよい。Ｒ_３はフッ素原子又はシアノ基であり、ｂは０〜４の整数である。
式（２）中、Ｒ_４は、フェニレン基又はシクロヘキシレン基であり、このフェニレン基又はシクロヘキシレン基の水素原子の一部又は全部は、炭素数１〜１０の鎖状又は環状のアルキル基、炭素数１〜１０の鎖状又は環状のアルコキシ基、フッ素原子又はシアノ基で置換されてもよい。Ｒ_５は、単結合、炭素数１〜３のアルキレン基、酸素原子、硫黄原子又は−ＮＨ−である。ｃは、１〜３の整数であり、ｃが２以上の場合、Ｒ_４及びＲ_５はそれぞれ同じでも異なっていてもよい。Ｒ_６は、フッ素原子又はシアノ基であり、ｄは０〜４の整数である。Ｒ_７は、酸素原子、−ＣＯＯ−＊又は−ＯＣＯ−＊（ただし、以上において「＊」を付した結合手がＲ_８と結合する）である。Ｒ_８は、２価の芳香族基、２価の脂環式基、２価の複素環式基又は２価の縮合環式基である。Ｒ_９は、単結合、−ＯＣＯ−（ＣＨ_２）_ｆ−＊又は−Ｏ（ＣＨ_２）_ｇ−＊（ただし、以上において「＊」を付した結合手がカルボキシル基と結合する）である。ｆ及びｇはそれぞれ１〜１０の整数であり、ｅは０〜３の整数である。） In the composition for organic semiconductor alignment, the group having the cinnamic acid structure is 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) It is preferable that one or both of the compound represented by the following formula (1) and the compound represented by the following formula (2) is also simply referred to as “specific cinnamic acid derivative”.

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

  By using the group derived from the specific cinnamic acid derivative as the group having the cinnamic acid structure, the anisotropy imparting performance to the organic semiconductor molecule, that is, the orientation performance is further improved. The definition of the stack becomes easy and the carrier mobility of the organic semiconductor layer can be further improved.

  In the organic semiconductor alignment composition, [A] the polyorganosiloxane compound having a photo-alignment group is selected from the group consisting of an epoxy group-containing polyorganosiloxane, a hydrolyzate thereof, and a condensate of the hydrolyzate. The reaction product is preferably a reaction product 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 the composition for organic semiconductor alignment, a specific cinnamic acid derivative having photo-alignment property on the polyorganosiloxane as a main chain by utilizing the reactivity between the polyorganosiloxane having an epoxy group and the specific cinnamic acid derivative Side chain groups derived from can be easily introduced.

（式（Ｘ_１−１）中、Ａは酸素原子又は単結合である。ｈは１〜３の整数であり、ｉは０〜６の整数である。ただし、ｉが０の場合、Ａは単結合である。
式（Ｘ_１−２）中、ｊは１〜６の整数である。
式（Ｘ_１−１）及び（Ｘ_１−２）中、「＊」は、それぞれ結合手であることを示す。） In the organic semiconductor alignment composition, 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 to 3, i is an integer of 0 to 6. However, when i is 0, A is It is a single bond.
Wherein _(X 1 -2), j is an integer from 1 to 6.
In the formulas (X ₁ -1) and (X ₁ -2), “*” represents a bond. )

By adopting the epoxy group represented by the above formula (X ₁ -1) or (X ₁ -2) as the epoxy group, the polyorganosiloxane of the composition for organic semiconductor alignment can be converted into the specific cinnamic acid derivative. It becomes easy to introduce the derived side chain group.

  The organic semiconductor alignment composition is selected from the group consisting of [B] carboxylic acid acetal ester structure, carboxylic acid ketal ester structure, carboxylic acid 1-alkylcycloalkyl ester structure and carboxylic acid t-butyl ester structure. It is preferable to further contain a compound having two or more of at least one kind of structure. When the composition for organic semiconductor alignment contains such a compound of the component [B] (hereinafter also simply referred to as “ester structure-containing compound”), a post-exposure baking step (hereinafter also referred to as “post-bake”). ), An acid is generated, and crosslinking of the polyorganosiloxane compound having a photo-alignment group can be promoted by the generated acid. As a result, the heat resistance of the obtained organic semiconductor alignment film can be improved.

  The organic semiconductor alignment film of the present invention is formed from the organic semiconductor alignment composition. As a result, the organic semiconductor alignment film exhibits excellent carrier mobility stability due to high heat resistance even after thermal load, and the orientation of the π-electron conjugate plane or π stack of organic semiconductor molecules is easy due to the photo-alignment group. Thus, excellent carrier mobility in the organic semiconductor layer can be expressed.

  The organic semiconductor device of the present invention includes a gate electrode formed on a substrate, an insulating film formed so as to cover the gate electrode, the organic semiconductor alignment film formed on the insulating film, and the organic semiconductor A source electrode and a drain electrode formed on the alignment film; and at least an organic semiconductor layer formed between the source electrode and the drain electrode. Since the organic semiconductor element employs the organic semiconductor alignment film as an alignment film for organic semiconductors, the organic semiconductor element can exhibit excellent photo-alignment sensitivity and reduce the amount of light irradiation, and the carrier in the organic semiconductor layer The mobility can be improved, and as a result, a high operating frequency and a high ON / OFF ratio in the organic semiconductor element can be achieved. In addition, since the organic semiconductor alignment film has high heat resistance, the initial carrier mobility can be maintained for a long time even after heat load.

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

  As described above, according to the composition for organic semiconductor alignment, the organic semiconductor alignment film, the organic semiconductor element, and the manufacturing method thereof according to the present invention, the photo-alignment sensitivity is good and the carrier mobility stability due to high heat resistance is realized. However, it is possible to exhibit excellent carrier mobility by orienting organic semiconductor molecules anisotropically at a high level.

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

  The composition for organic semiconductor alignment of the present invention contains [A] a polyorganosiloxane compound having a photo-alignment group (hereinafter, also simply referred to as “photo-alignment polyorganosiloxane compound”). The light irradiation amount necessary for orientation can be reduced by the property. Moreover, by using the composition for organic semiconductor alignment, the obtained organic semiconductor alignment film exhibits high heat resistance, thereby exhibiting high carrier mobility stability after heat load. In addition, since this organic semiconductor alignment film has an excellent photo-alignment property, an anisotropic alignment at a high level in the organic semiconductor layer can be expressed.

  The composition for aligning an organic semiconductor contains [A] a photo-alignable polyorganosiloxane compound, may contain a [B] ester structure-containing compound as a suitable component, and as other optional components. , At least one polymer selected from the group consisting of polyamic acid and polyimide, a polymer other than the photoalignable polyorganosiloxane compound (hereinafter referred to as “other polymer”), a curing agent, a curing catalyst, and curing. An accelerator, a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), a functional silane compound, a surfactant, a photosensitizing compound, and the like may be included. Hereinafter, the organic semiconductor alignment composition will be described.

[A] component: polyorganosiloxane compound having photoalignable group [A] In the polyorganosiloxane compound having photoalignable group, polyorganosiloxane as a main chain, its hydrolyzate, and condensate of its hydrolyzate A photo-alignment group is introduced as a side chain in a portion derived from at least one selected from the group consisting of: When an organic semiconductor alignment film is formed with the organic semiconductor alignment composition, if this photo-alignment group is irradiated with light having anisotropy such as polarized light, the rearrangement of molecules and the difference in the alignment within the organic semiconductor alignment film are caused. Induces a chemical reaction with anisotropy. Anisotropy is imparted to the organic semiconductor molecule by the change in the molecular structure of the alignment film accompanied by this anisotropy. Moreover, the photo-alignment group and the polyorganosiloxane compound improve the photo-alignment sensitivity, and can realize a low light irradiation amount. At the same time, since polyorganosiloxane is adopted as the main chain, the organic semiconductor alignment film formed from the organic semiconductor alignment composition has excellent chemical stability and thermal stability and high heat resistance. Therefore, the carrier mobility can be maintained for a long time even after the heat load.

Photo-Orienting Group As described above, the photo-orienting group induces a change in the microscopic structure of the molecules constituting the alignment film by irradiation with anisotropic light. Such a photoalignment group is not particularly limited, and groups derived from various compounds exhibiting photoalignment can be employed. The mechanism of anisotropy expression in the photo-alignment group is roughly divided into a photoreactive type and a photoisomerization type. The photoreactive type is further classified into a dimerization type, a decomposition type, a bond type, and a decomposition cross-linking type. From the viewpoint of preventing the organic semiconductor layer from being contaminated, those in which impurity ions, radicals and the like do not remain after light irradiation are preferable, and therefore, a photoisomerization type and a dimerization type are preferable.

  Specific examples of the photoalignable group include, for example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton, a chalcone or a derivative thereof as a basic skeleton As a chalcone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing a polyimide or a derivative thereof as a basic skeleton, etc. It is done. Among these photo-orientable groups, a group having a cinnamic acid structure that exhibits dimerization-type anisotropy and takes high orientation ability and ease of introduction into consideration, contains cinnamic acid or a derivative thereof as a basic skeleton. preferable. Cinnamic acid or a derivative thereof may be cis type or trans type as long as it can be dimerized by light irradiation.

The structure of the 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 the compound represented by the above formula (1) and the compound represented by the above formula (2) It is preferably a group derived from at least one of the specific cinnamic acid derivatives. In the above formula (1), R ₁ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group, and part or all of the hydrogen atoms of the phenylene, biphenylene group, terphenylene group or cyclohexylene group May be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom as a substituent, a fluorine atom or a cyano group. R ₂ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, —CH═CH—, —NH— or —COO—. a is an integer of 0 to 3, and when a is 2 or more, R ₁ and R ₂ may be the same or different. R ₃ is a fluorine atom or a cyano group, and b is an integer of 0 to 4.

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

Among these, R ₁ is preferably an unsubstituted phenylene group or a phenylene group substituted with a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and R ₂ is a single bond, an oxygen atom or —CH ₂ ═CH _2. What is-is preferable. b is preferably 0 to 1, and when a is 1 to 3, b is particularly preferably 0.

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

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

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

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

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

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

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

  [A] The polyorganosiloxane compound having a photo-alignment group is at least one selected from the group consisting of a polyorganosiloxane having an epoxy group, a hydrolyzate thereof, and a condensate of the hydrolyzate (hereinafter simply referred to as “ It is preferably a reaction product of a compound represented by the above formula (1) and / or (2) with a polyorganosiloxane having an epoxy group. In the composition for organic semiconductor alignment, a specific cinnamic acid derivative having photo-alignment property on the polyorganosiloxane as a main chain by utilizing the reactivity between the polyorganosiloxane having an epoxy group and the specific cinnamic acid derivative The group derived from can be easily introduced.

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

（式（３）中、Ｘ_１はエポキシ基を有する１価の有機基であり、Ｙ_１は水酸基、炭素数１〜１０のアルコキシ基、炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基である。）

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

  The hydrolysis condensate of the polyorganosiloxane having the repeating unit represented by the above formula (3) is not only the hydrolysis condensate of the polyorganosiloxane but also the repeating unit represented by the above formula (3). Hydrolysis condensate in the case where the polyorganosiloxane obtained by branching or cross-linking of the main chain has a repeating unit represented by the above formula (3) in the process of producing polyorganosiloxane by hydrolytic condensation of It is a concept that also includes

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

（上記式中、「＊」は結合手であることを示す。）
で表される基が好ましい。

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

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

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

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

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

  Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, and trichlorosilane. Methoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluoro Tri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyl Triethoxysilane, methyl tri -n- propoxysilane, methyltri -i- propoxysilane, methyltri -n- butoxysilane, methyltri -sec- butoxysilane, 2- (trifluoromethyl) ethyl trichlorosilane,

  2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxy Silane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro- n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ) Ethyltri-i-propoxysilane, 2- (par Fluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2- (perfluoro- n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane,

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

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

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

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

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

  Of these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth), from the viewpoint of the orientation and chemical stability of the resulting organic semiconductor alignment film. Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3 -Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane are preferred. There.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  [A] The photo-alignable polyorganosiloxane compound is a hydrolysis product obtained by hydrolyzing and condensing a portion derived from a hydrolyzate produced by hydrolysis of an epoxy group-containing polyorganosiloxane itself or an epoxy group-containing polyorganosiloxane. A portion derived from the condensate may be included. These hydrolyzates and hydrolysis condensates which are constituent materials of the part can also be prepared in the same manner as the hydrolysis or condensation conditions of polyorganosiloxane having an epoxy group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The compound represented by the above formula (4) can contribute to improving the stability of the composition for aligning organic semiconductors by deactivating the active site of the photoalignable polyorganosiloxane compound [A]. In the present invention, when the compound represented by the above formula (4) is used together with the specific cinnamic acid derivative, the total use ratio of the specific cinnamic acid derivative and the compound represented by the above formula (4) is that of the polyorganosiloxane. Preferably it is 0.001-1.5 mol with respect to 1 mol of epoxy groups to have, More preferably, it is 0.01-1 mol, More preferably, it is 0.05-0.9 mol. In this case, the compound represented by the formula (4) is preferably used in a range of 50 mol% or less, more preferably 25 mol% or less, based on the total with the specific cinnamic acid derivative. When the use ratio of the compound represented by the above formula (4) exceeds 50 mol%, there is a possibility of causing a problem that the orientation in the organic semiconductor alignment film is lowered.

[B] component: ester structure-containing compound The organic semiconductor alignment composition can form an organic semiconductor alignment film excellent in heat resistance and light resistance by including the [B] ester structure-containing compound, and the organic semiconductor alignment The storage stability of the composition for use can be improved.

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

（式（Ｂ−１）中、Ｒ_１３及びＲ_１４は、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数３〜１０の脂環式基、炭素数６〜１０のアリール基又は炭素数７〜１０のアラルキル基であり、
式（Ｂ−２）中、ｎ１は２〜１０の整数である。）

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

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

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

Examples of the group represented by the formula (B-2) include a 2-tetrahydrofuranyloxycarbonyl group, a 2-tetrahydropyranyloxycarbonyl group, and the like.

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

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

（式（Ｂ−３）中、Ｒ_１５は炭素数１〜１２のアルキル基であり、Ｒ_１６及びＲ_１７は、それぞれ独立して、炭素数１〜１２のアルキル基、炭素数３〜２０の脂環式基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基である。
式（Ｂ−４）中、Ｒ_１８は炭素数１〜１２のアルキル基であり、ｎ２は２〜８の整数である。
式（Ｂ−５）中、Ｒ_１９は炭素数１〜１２のアルキル基であり、ｎ３は２〜８の整数である。）

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

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

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

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

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

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

（式（Ｂ−６）中、Ｒ_２０は炭素数１〜１２のアルキル基であり、ｎ４は１〜８の整数である。）

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

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

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

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

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

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

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

  In the case where n is 3, the following formula

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

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

For example, a compound in which the group B in the formula (B) is a group represented by the formula (B-1) (except for the case where R ₁₃ is a phenyl group) is preferably in the presence of a phosphoric acid catalyst. And compound R- (COOH) _n (wherein R and n have the same meanings as in formula (B) above) and compound R ₁₄ —O—CH═R _{13 ′} (where R ₁₄ is the formula above) (B-1) and R _{13 ′} is a group obtained by removing a hydrogen atom from the 1-position carbon of the group R ₁₃ in the above formula (B-1). Can be synthesized.

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

（式中、ｎ１は上記式（Ｂ−２）におけるのと同義である。）

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

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

At least one polymer selected from the group consisting of polyamic acid and polyimide The composition for aligning organic semiconductors may contain at least one polymer selected from the group consisting of polyamic acid and polyimide. When the composition contains this polymer, the thermal alignment and chemical stability of the obtained alignment film for organic semiconductor are increased, and the adhesion to the insulating layer is improved.
Hereinafter, at least one polymer selected from the group consisting of polyamic acid and polyimide will be described in the order of polyamic acid and polyimide.

Polyamic acid The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.
Examples of tetracarboxylic dianhydrides that can be used for the synthesis of polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydride) -2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, the following formula (F-1) ~ (F-14)

のそれぞれで表されるテトラカルボン酸二無水物等の脂肪族又は脂環式テトラカルボン酸二無水物；
ピロメリット酸二無水物、３，３’，４，４’−ビフェニルスルホンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−ジメチルジフェニルシランテトラカルボン酸二無水物、３，３’，４，４’−テトラフェニルシランテトラカルボン酸二無水物、１，２，３，４−フランテトラカルボン酸二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルフィド二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルホン二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルプロパン二無水物、３，３’，４，４’−パーフルオロイソプロピリデンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ビス（フタル酸）フェニルホスフィンオキサイド二無水物、ｐ−フェニレン−ビス（トリフェニルフタル酸）二無水物、ｍ−フェニレン−ビス（トリフェニルフタル酸）二無水物、ビス（トリフェニルフタル酸）−４，４’−ジフェニルエーテル二無水物、ビス（トリフェニルフタル酸）−４，４’−ジフェニルメタン二無水物、下記式（Ｆ−１５）〜（Ｆ−１８）

An aliphatic or alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of
Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide Dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′ , 4 4′-perfluoroisopropylidenetetracarboxylic 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 formulas (F-15) to (F-18)

のそれぞれで表されるテトラカルボン酸二無水物等の芳香族テトラカルボン酸二無水物等を挙げることができる。

An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the above.

  Among these, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1, 3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c] -furan-1 , 3-dione, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-Cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarbo Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, or the above formula (F-1), ( Examples thereof include tetracarboxylic dianhydrides represented by F-2) and (F-15) to (F-18). These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Examples of the diamine compound that can be used for the synthesis of polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diaminodiphenyl sulfide. 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 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-trimethylindane, 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- Diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-methylene-bis (2-chloroaniline), 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) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-amino-2-trifluoro) Methylphenoxy) 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-chalconi) Ruoxy) hexyloxy (2,4-diaminobenzene), 8- (4-calconyloxy) octyloxy (2,4-diaminobenzene), 8- (4′-fluoro-4-calconyloxy) octyloxy ( 2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyl Oxy-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), pentadecyl Oxy (3,5-diaminobenzoyl), hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,3) 5-Diaminobenzoyl), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) stearate, (2,4-diaminophenoxy) -4-trifluoromethylbenzoate, the following formula (G-1) ~ (G-5)

のそれぞれで表されるジアミン化合物等の芳香族ジアミン；

An aromatic diamine such as a diamine compound represented by each of

An aromatic diamine having a heteroatom such as diaminotetraphenylthiophene;
Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diamino Cyclohexane, cyclohexanebis (methylamine), tetrahydrodicyclopentadienylenediamine, isophoronediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl Aliphatic or alicyclic diamines such as diamine, 4,4′-methylenebis (cyclohexylamine);
Examples include diaminoorganosiloxanes such as diaminohexamethyldisiloxane.

  Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-2,2′-dimethylbiphenyl, cyclohexanebis (methylamine), 1,5-diaminonaphthalene, 2 , 7-diaminofluorene, 4,4′-diaminodiphenyl ether, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 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 ′ -Bis (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 diamines represented by the above formulas (G-1) to (G-5). These diamines can be used alone or in combination of two or more.

  The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.

  The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 to 10 Done for hours. Here, 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-dimethylformamide, 1, Aprotic polar solvents such as 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol Can be mentioned. The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is preferably 0.1 to 50% by mass, more preferably 5%, based on the total amount (a + b) of the reaction solution. The amount is -30% by mass.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the composition for organic semiconductor alignment, or may be used for the preparation of the composition for organic semiconductor alignment after isolating the polyamic acid contained in the reaction solution. You may use for the preparation of the composition for organic-semiconductor orientation, after refine | purifying the polyamic acid which did. The polyamic acid is isolated by pouring the 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 of the reaction solution under reduced pressure using an evaporator. be able to. The polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of distilling off under reduced pressure with an evaporator once or several times.

Polyimide The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good.

  The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.

  The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. By setting the reaction temperature to 50 ° C. or higher, the dehydration ring-closing reaction can be sufficiently advanced, and by setting the reaction temperature to 200 ° C. or lower, it is possible to suppress a decrease in the molecular weight of the resulting imidized polymer. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

  On the other hand, in the above method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid structural unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. 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-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

  In the method (ii), a reaction solution containing polyimide is thus obtained. This reaction solution may be used as it is for preparing a composition for aligning organic semiconductors, or may be used for preparing a composition for aligning organic semiconductors after removing a dehydrating agent and a dehydrating ring-closing catalyst from the reaction solution. The isolated polyimide may be used for the preparation of an organic semiconductor alignment composition, or the isolated polyimide may be purified and then used for the preparation of an organic semiconductor alignment composition. In order to remove the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operations as described above as the method for isolating and purifying the polyamic acid.

  In the composition for aligning organic semiconductors of the present invention, in addition to the photo-alignable polyorganosiloxane compound, in the case of containing at least one polymer selected from the group consisting of polyamic acid and polyimide, the preferred use ratio of both is The total amount of polyamic acid and polyimide is 100 to 5,000 parts by mass, and more preferably 200 to 2,000 parts by mass with respect to 100 parts by mass of the photoalignable polyorganosiloxane compound.

Other Polymers The other polymers described above can be used to further improve the solution characteristics of the composition for aligning organic semiconductors of the present invention and the electrical characteristics of the resulting organic semiconductor alignment film. Such other polymer is selected from the group consisting of, for example, a polyorganosiloxane having a repeating unit having a structure different from the repeating unit represented by the above formula (3), a hydrolyzate thereof, and a condensate of the hydrolyzate. At least one kind (hereinafter referred to as “other polyorganosiloxane”), polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, etc. Can be mentioned.

Other Polyorganosiloxane The composition for organic semiconductor alignment of the present invention may contain other polyorganosiloxane in addition to the photo-alignable polyorganosiloxane compound as described above. When other polyorganosiloxane is contained in the present invention, at least one selected from the group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (5), a hydrolyzate thereof, and a condensate of the hydrolyzate. Preferably it is a seed.

（式（５）中、Ｘ_２は水酸基、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数１〜６のアルコキシ基又は炭素数６〜２０のアリール基であり、Ｙ_２は水酸基又は炭素数１〜１０のアルコキシ基である。）

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

  When the organic semiconductor alignment composition contains other polyorganosiloxane, most of the other polyorganosiloxane is present independently from the photo-alignable polyorganosiloxane compound, part of which May exist as a condensate with a photoalignable polyorganosiloxane compound.

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

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

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

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

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

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and di-i-. Monoketone compounds such as butyl ketone, methyl-n-hexyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, fenchon, acetophenone, acetonylacetone;
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, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. The β-diketone compound and the like can be mentioned respectively. These ketone compounds may be used alone or in combination of two or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

When the composition for organic semiconductor alignment of the present invention contains another polymer together with the above-mentioned photo-alignable polyorganosiloxane compound, the content of the other polymer is as follows: It is preferable that it is 10,000 mass parts or less with respect to 100 mass parts of photo-alignment polyorganosiloxane compounds. The more preferable content of the other polymer varies depending on the type of the other polymer.

  On the other hand, when the composition for aligning an organic semiconductor of the present invention contains a photoalignable polyorganosiloxane compound and another polyorganosiloxane, the preferred use ratio of both is 100 mass of the photoalignable polyorganosiloxane compound. The amount of other polyorganosiloxane with respect to parts is 100 to 2,000 parts by mass. When the composition for aligning an organic semiconductor of the present invention contains another polymer together with the photoalignable polyorganosiloxane compound, the other polymer is preferably another polyorganosiloxane. .

Curing Agent, Curing Catalyst, and Curing Accelerator The curing agent and the curing catalyst can be included in the composition for aligning organic semiconductors of the present invention for the purpose of strengthening the crosslinking reaction of the photoalignable polyorganosiloxane compound. . The said hardening accelerator can be included in the composition for organic-semiconductor orientation of this invention in order to accelerate | stimulate the hardening reaction which a hardening | curing agent controls.

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

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

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

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

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

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

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

Epoxy Compound The above epoxy compound may be included in the composition for aligning organic semiconductors of the present invention from the viewpoint of improving the adhesion of the formed organic semiconductor alignment film to the insulating film surface.

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

  When the composition for organic semiconductor alignment of the present invention contains an epoxy compound, the content is 100 parts by mass in total of the photo-alignable polyorganosiloxane compound and other polymers optionally used. On the other hand, it is preferably 0.01 to 40 parts by mass, and more preferably 0.1 to 30 parts by mass.

  In addition, when the composition for organic-semiconductor orientation of this invention contains an epoxy compound, you may use together basic catalysts, such as 1-benzyl-2-methylimidazole, in order to raise | generate the crosslinking reaction efficiently.

Functional silane compound The functional silane compound can be used for the purpose of improving the adhesion of the resulting organic semiconductor alignment film to the substrate or gate electrode. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane In addition, JP-A 3 over is described in 291922 JP, it may be mentioned the reaction products of a silane compound having a tetracarboxylic dianhydride and an amino group.

  When the composition for organic semiconductor alignment of the present invention contains a functional silane compound, the content is 100 mass in total of the above-mentioned photo-alignable polyorganosiloxane compound and other polymers optionally used. Preferably it is 50 mass parts or less with respect to a part, More preferably, it is 20 mass parts or less.

Surfactant Examples of the surfactant include, for example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. Can be mentioned.

  When the composition for organic semiconductor alignment contains a surfactant, the content is preferably 10 parts by mass or less, more preferably 1 with respect to 100 parts by mass as a whole of the composition for organic semiconductor alignment. It is below mass parts.

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

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

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

（式中、ｑは１〜６の整数である。）

(Wherein q is an integer of 1 to 6)

  The photo-alignment polyorganosiloxane compound used in the present invention is preferably combined with the photo-sensitizing compound in addition to the polyorganosiloxane having an epoxy group and the specific cinnamic acid derivative, preferably in the presence of a catalyst. May be synthesized by reacting in an organic solvent. In this case, the specific cinnamic acid derivative is preferably 0.001 to 1 mol, more preferably 0.1 to 1 mol, still more preferably 0.2 to 1 mol of the silicon atom of the polyorganosiloxane having an epoxy group. Used in the range of ~ 0.9 mol. The photosensitizing compound is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, still more preferably 0.001 mol per mol of silicon atom of the polyorganosiloxane having an epoxy group. It is used in the range of 001 to 0.1 mol.

Preparation of organic semiconductor alignment composition The organic semiconductor alignment composition of the present invention contains a photo-alignable polyorganosiloxane compound as an essential component as described above, and additionally contains other components as necessary. However, it is preferably prepared as a solution composition in which each component is dissolved in an organic solvent. The photoalignable polyorganosiloxane compound and other components (for example, at least one polymer selected from the group consisting of polyamic acid and polyimide, and other polyorganosiloxane) are organic semiconductor alignment compositions. In any state of the product and the organic semiconductor alignment film, they may be partially bonded to each other.

  As an organic solvent that can be used for preparing the composition for aligning organic semiconductors of the present invention, a solvent that dissolves and does not react with the photo-alignable polyorganosiloxane compound and other components used is preferable. . The organic solvent that can be preferably used in the composition for aligning organic semiconductors of the present invention varies depending on the type of other polymer that is optionally added.

  In the composition for aligning organic semiconductors of the present invention, examples of a preferable organic solvent for the photoalignable polyorganosiloxane compound include the organic solvents exemplified above as those used for the synthesis of polyamic acid. At this time, you may use together the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention. These organic solvents can be used alone or in combination of two or more.

  On the other hand, as a preferred organic solvent when the composition for aligning organic semiconductors of the present invention contains a photoalignable polyorganosiloxane compound and another polyorganosiloxane as a polymer, for example, 1-ethoxy-2-propanol, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether Ter (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 carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, Examples include 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, and isoamyl acetate. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate and the like can be mentioned.

  The preferable solvent used for the preparation of the composition for aligning organic semiconductors of the present invention can be obtained by combining one or more of the above-mentioned organic solvents according to whether or not other polymers are used and their types. In such a solvent, each component contained in the composition for organic semiconductor alignment does not precipitate at the following preferable solid content concentration, and the surface tension of the composition for organic semiconductor alignment is in the range of 25 to 40 mN / m. Is.

  The solid content concentration of the composition for organic semiconductor alignment of the present invention, that is, the ratio of the mass of all components other than the solvent in the composition for organic semiconductor alignment to the total mass of the composition for organic semiconductor alignment is viscosity, volatility, etc. However, it is preferably in the range of 1 to 10% by mass. The composition for aligning an organic semiconductor of the present invention is applied onto an insulating film to form a coating film to be an organic semiconductor alignment film. When the solid content concentration is 1% by mass or more, the coating film is formed. It is difficult to make the thickness excessively small, and a good organic semiconductor alignment film can be obtained. On the other hand, when the solid content concentration is 10% by mass or less, it is possible to obtain an excellent organic semiconductor alignment film by suppressing the film thickness of the coating film from being excessively large. It is possible to prevent the viscosity from increasing and to improve the coating characteristics. The particularly preferable range of the solid content concentration varies depending on the method employed when applying the organic semiconductor alignment composition to the insulating film. For example, when the spinner method is used, the range of 1.5 to 4.5% by mass is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by mass, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.

  The temperature for preparing the composition for aligning organic semiconductors of the present invention is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

Organic Semiconductor Alignment Film The organic semiconductor alignment composition of the present invention is suitable for forming an alignment film that imparts anisotropy to an organic semiconductor layer by a photo-alignment method, particularly an alignment film used for a field effect organic semiconductor element. Can be used for

  As a method for forming the organic semiconductor alignment film, for example, an insulating film is formed on a substrate on which a gate electrode is formed, and a coating film is formed on the insulating film using the composition for aligning an organic semiconductor of the present invention. Examples thereof include a method for imparting organic semiconductor molecule alignment ability by a photo-alignment method in which the coating film is irradiated with anisotropic polarized light or the like.

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

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

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

Although it does not specifically limit as an irradiation amount of light, Preferably it is 1 J / m < ² > or more and less than 10,000 J / m < ² >, More preferably, it is 10-3,000 J / m < ² >. In addition, when providing the organic semiconductor molecular orientation ability by the photo-alignment method to the coating film formed from the conventionally known composition for organic-semiconductor orientation, the light irradiation amount of 10,000 J / m < ² > or more was required. . However, when the composition for aligning organic semiconductors of the present invention is used, good organic semiconductor molecular alignment is possible even when the radiation dose in the photo-alignment method is 3,000 J / m ² or less, and even 1,000 J / m ² or less. Performance, which contributes to the improvement of the productivity of organic semiconductor elements and the reduction of manufacturing costs.

  In applying the organic semiconductor alignment composition, a functional silane compound, titanate, or the like may be applied in advance on the insulating film in order to further improve the adhesion between the insulating film and the coating film. Good.

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

  When a voltage (source-drain voltage) is applied between the source electrode 6 and the drain electrode 7 of the organic semiconductor element and the voltage applied to the gate electrode 3 (gate voltage: Vg) is changed, the voltage depends on the gate voltage. As a result, the amount of charge (carrier) at the interface between the organic semiconductor layer 8 and the alignment film 5 changes, and the current (source−) flows through the portion (channel) of the organic semiconductor layer 8 between the source electrode 6 and the drain electrode 7. The drain-to-drain current) can be changed. Thus, in the organic semiconductor element, the drain current Id can be controlled by controlling the gate voltage Vg.

  There is a close relationship between the π-orbit conjugate plane or π stack of the organic semiconductor material and the carrier movement direction. In order to improve the carrier mobility μ in the organic semiconductor layer, it is important not only to align the direction of the organic semiconductor molecules in a certain direction but also to define a π orbital conjugate plane or π stack. In the organic semiconductor element of the present invention, the alignment film is aligned by a photo-alignment method, thereby giving anisotropy to the alignment of the organic semiconductor molecules. π stack can be defined, organic semiconductor alignment film with excellent flatness without alignment unevenness can be formed, and furthermore, the problem of rubbing scratches and contamination adhesion due to rubbing can be solved and off current can be suppressed. it can.

  The insulating substrate is not particularly limited. For example, in addition to inorganic materials such as glass and quartz, photosensitive polymer compounds such as acrylic, vinyl, ester, imide, urethane, diazo, and cinnamoyl, polyfluoride Organic materials such as vinylidene, polyethylene terephthalate, and polyethylene, and organic-inorganic hybrid materials can be used. In addition, two or more layers of these materials can be used, which is effective for increasing the withstand voltage.

The gate insulating film formed by the organic semiconductor element of the present invention may be a single layer or two or more layers, and various known materials may be used in combination. Is not particularly restricted but includes known materials _{SiO 2, SiN, Al 2 O} 3, Ta 2 O 5 or the like of inorganic materials, polyamic acid, polyimide, polyacrylonitrile, polytetrafluoroethylene, polyvinyl alcohol, polyvinyl phenol, polyethylene terephthalate Organic materials such as polyvinylidene fluoride and organic-inorganic hybrid materials can be used. Preferably, an organic material is preferable from the viewpoint that a liquid phase process leading to low cost can be used. In addition, as said polyamic acid and a polyimide, the said polyamic acid and polyimide which may be contained in the said composition for organic-semiconductor orientation can be used.

The organic semiconductor molecule constituting the organic semiconductor layer of the organic semiconductor element of the present invention is not particularly limited as long as it is a conjugated compound having a conjugated double bond. For example, the following compounds are suitable:
Polyacetylene derivatives, polythiophene derivatives having a thiophene ring, poly (3-alkylthiophene) derivatives, poly (3,4-ethylenedioxythiophene) derivatives, polythienylene vinylene derivatives, polyphenylene derivatives having a benzene ring, polyphenylene vinylene derivatives, nitrogen Conjugated polymer compounds such as polypyridine derivatives having atoms, polypyrrole derivatives, polyaniline derivatives, polyquinoline derivatives;
Oligomers typified by dimethylsexithiophene and quarterthiophene;
Acenes represented by perylene, tetracene and pentacene;
Deposited organic molecules represented by copper phthalocyanine derivatives;
Discotic liquid crystal typified by triphenylene derivatives;
Smectic liquid crystals typified by phenylnaphthalene derivatives and benzothiazole derivatives; and liquid crystal polymers typified by poly (9,9-dialkylfluorene-bithiophene) copolymers;
Etc. However, the organic semiconductor molecule is not limited to these.

  Among these organic semiconductor molecules, the polymer compound having the above conjugated structure is preferable from the viewpoint that a liquid phase process can be used. The molecular weight of these conjugated polymer compounds is not particularly limited, but the mass average molecular weight is preferably 5,000 to 500,000 in consideration of solubility in a solvent, film formability, and the like.

The organic semiconductor layer used in the organic semiconductor element may contain an appropriate dopant in order to adjust the electric conductivity. Acceptor type I ₂ , Br ₂ , Cl ₂ , ICl, BF ₃ , PF ₅ , H ₂ SO ₄ , FeCl ₃ , TCNQ (tetracyanoquinodimethane), donor-type Li, K, Na, Eu, surfactant alkyl sulfonate, alkyl benzene sulfonate, and the like.

The gate electrode, the source electrode, and the drain electrode used in the organic semiconductor element of the present invention are not particularly limited as long as they are conductors. Examples of the constituent material of each electrode include metal materials such as Al, Cu, Ti, Au, Pt, Ag, and Cr, inorganic materials such as polysilicon, silicide, ITO (Indium Tin Oxide), SnO ₂ , and highly doped polypyridine. In addition, conductive polymer materials represented by polyacetylene, polyaniline, polypyrrole, polythiophene, and conductive ink in which carbon particles, silver particles, and the like are dispersed can be used. In particular, when used for 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, and the like are dispersed, so that thermal expansion properties with the substrate can be easily aligned.

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

  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. For example, an electrolytic polymerization method, a casting method, a spin coating method, a screen printing method, a dip coating method, a micromold method, It can be formed by a micro contact method, an ink jet method, a roll coating method, an LB method or the like. As for a method for forming each electrode, a vacuum vapor deposition method, a CVD method, an electron beam vapor deposition method, a resistance heating vapor deposition method, a sputtering method, or the like can be employed depending on the material to be used.

  These can be patterned into a desired shape by photolithography and etching. In addition, soft lithography and ink jet methods are also effective patterning methods. Moreover, the extraction electrode from each electrode, a protective film, etc. can be formed as needed.

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

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

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

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

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

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

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

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

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

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

[A] Synthesis of photoalignable polyorganosiloxane compound [Synthesis Example 7]
In a 100 mL three-necked flask, 9.3 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 26 g of methyl isobutyl ketone, 3 g of the specific cinnamic acid derivative (K-1) obtained in Synthesis Example 2 above, and the trade name “ 0.10 g of “UCAT 18X” (a quaternary amine salt manufactured by San Apro Co., Ltd.) was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. This solution was washed with water three times, and then the solvent was distilled off to remove the photoalignable polyorganosiloxane compound (S -1) was obtained as a white powder. The photoalignable polyorganosiloxane compound (S-1) had a mass average molecular weight Mw of 3,500.

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

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

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

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

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

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

[Synthesis Example 12]
A 500 mL three-necked flask equipped with a reflux tube, a thermometer, and a nitrogen introduction tube was charged with 21 g of trimesic acid, 60 g of n-butyl vinyl ether and 0.09 g of phosphoric acid, and reacted at 50 ° C. with stirring for 30 hours. After completion of the reaction, the organic layer obtained by adding 500 mL of hexane to the reaction mixture was separated and washed successively with 1M aqueous sodium hydroxide solution twice and water three times. Then, 50g of ester structure containing compounds (B-1-1) were obtained as a colorless and transparent liquid by distilling a solvent off from an organic layer.

Polyamic acid was used as a material constituting the synthetic insulating film of polyamic acid, and was synthesized by the following procedure.
[Synthesis Example 13]
Cyclobutanetetracarboxylic dianhydride 19.61 g (0.1 mol) and 4,4′-diamino-2,2′-dimethylbiphenyl 21.23 g (0.1 mol) were combined with N-methyl-2-pyrrolidone 367. Dissolved in 6 g and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 35 g of polyamic acid (PA-1).

Preparation of organic semiconductor alignment composition <Example 1>
In a solvent whose composition is N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio), 100 parts by mass of the photoalignable polyorganosiloxane compound (S-1) obtained in Synthesis Example 7 is dissolved, It was set as the solution whose solid content concentration is 4.0 mass%. The solution for organic semiconductor alignment (A-1) was prepared by filtering this solution with a filter having a pore diameter of 1 μm.

<Examples 2 to 5>
Various compositions for organic semiconductor alignment (A-2) to (A-5) were prepared in the same manner as in Example 1 by changing the photoalignable polyorganosiloxane compound. In Example 4, 5 parts by mass of the ester structure-containing compound (B-1-1) obtained in Synthesis Example 12 was further added to 100 parts by mass of the photoalignable polyorganosiloxane compound, and organic semiconductor alignment was performed. A composition was prepared. These formulations are shown in Table 1.

<Comparative Example 1>
After dissolving 13.1 g of poly (2-hydroxyethyl methacrylate) in 50 ml of N-methyl-2-pyrrolidone and cooling to room temperature, 10 ml of pyridine was added. To this, 17.0 g of cinnamoyl chloride was added and stirred for 8 hours. The reaction mixture was diluted with N-methyl-2-pyrrolidone and added to methanol, and the precipitate was sufficiently washed with water and dried to obtain 25 g of a polymer. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to obtain a solution having a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio) and a solid content concentration of 4.0% by mass. The solution (CA-1) was prepared by filtering this solution through a filter having a pore size of 1 μm.

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

Formation of an organic semiconductor alignment film and formation of an organic semiconductor element A gate electrode having a thickness of 20 nm was formed on a glass substrate by a vacuum deposition method using Al as an electrode material. Thereafter, the polyamic acid (PA-1) prepared in Synthesis Example 13 was applied by a spinner, and heated (baked) at 200 ° C. for 1 hour in an oven in which the inside of the chamber was purged with nitrogen. Formed. Next, on this insulating film, the organic semiconductor alignment composition (A-1) prepared in Example 1 was applied with a spinner, pre-baked on a hot plate at 80 ° C. for 1 minute, and then the interior was replaced with nitrogen. Was heated in an oven at 200 ° C. for 1 hour (post-baking) to form a coating film having a thickness of 0.1 μm. The spinner rotation speed was 2000 rotations and the solid content concentration of the alignment film solvent was 4.0 mass% so that the film thickness after formation was 0.1 μm. Next, the surface of the coating film was irradiated with linearly polarized ultraviolet rays including a 13 nm emission line perpendicularly from the substrate normal line using an Hg—Xe lamp and a Glentaler prism to form an organic semiconductor alignment film. The amount of light irradiation required for the orientation of the photoalignable group in the coating film formed at this time was measured and used as an index of the photoalignment sensitivity. The orientation of the photoalignable group was confirmed using a polarizing microscope.

  Next, source and drain electrodes were formed on the organic semiconductor alignment film by gold vapor deposition, and the channel length was 30 μm and the channel width was 50 μm. Next, an organic semiconductor molecular film having a thickness of 700 mm of modified pentacene was formed by vapor deposition so as to cover both electrodes, and a top gate type organic semiconductor element was manufactured.

  The organic semiconductor element was produced similarly about the composition prepared in Examples 2-5 and Comparative Examples 1-2. These organic semiconductor elements were evaluated by the following methods. The evaluation results are shown in Table 1.

Evaluation of Organic Semiconductor Element (1) Evaluation of Initial Carrier Mobility For the top gate type organic semiconductor element manufactured by the above procedure, the initial carrier mobility was measured using a semiconductor parameter analyzer (Semiconductor parameter analyzer HP4155a, manufactured by Hewlett-Packard Company). It was measured.

(2) Evaluation of carrier mobility after thermal load The organic semiconductor element was placed under heating conditions, and the carrier mobility after thermal load was measured to evaluate the stability against heat. Specifically, the top gate type organic semiconductor device produced by the above procedure is heated in an oven set at 70 ° C. for 500 hours, and then heated by the same procedure as in “(1) Evaluation of initial carrier mobility”. The carrier mobility after loading was measured. The evaluation results are shown in Table 1. In addition, Table 1 also shows the carrier mobility maintenance rate after thermal load.

As is clear from the results in Table 1, in the compositions for aligning organic semiconductors of Examples 1 to 5, the amount of light irradiation required for photoalignment when producing an organic semiconductor alignment film using them is extremely low. The sensitivity of was good. Further, in the organic semiconductor element provided with the alignment film, high carrier mobility is achieved, and in the organic semiconductor element, the initial carrier mobility is maintained at a high rate even after heat load, and excellent heat resistance is achieved. The result was obtained. On the other hand, in the alignment film produced using the composition of Comparative Example 1, the photo-alignment sensitivity and the carrier mobility of the semiconductor element were good, but the carrier mobility after thermal load was about half the value. It was inferior in heat resistance. The alignment film produced using the composition of Comparative Example 2 requires 20000 J / m ² as the light irradiation amount of the photo-alignment, and the carrier mobility is half the carrier mobility of the organic semiconductor element of the example. The result was below.

  Since the composition for aligning organic semiconductors of the present invention contains a photoalignable polyorganosiloxane compound, as described above, the photoalignment sensitivity is good, and the carrier mobility after heat load is stable. In an organic semiconductor device having an organic semiconductor alignment film, the anisotropic alignment of organic semiconductor molecules can be induced at a high level by the photo-alignment group on the surface of the organic semiconductor alignment film. Mobility can be achieved.

1 Organic Semiconductor Element 2 Substrate 3 Gate Electrode 4 Gate Insulating Film 5 Alignment Film for Organic Semiconductor 6 Source Electrode 7 Drain Electrode 8 Organic Semiconductor Layer

Claims (7)

[A] Photo-alignment comprising at least one cinnamic acid structure 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 the following formula (2) The composition for organic-semiconductor alignment containing the polyorganosiloxane compound which has a functional group.

(In the formula (1), R ₁ is a phenylene group, a biphenylene group, a terphenylene group or a cyclohexylene group, and a part or all of the hydrogen atoms of the phenylene, biphenylene group, terphenylene group or cyclohexylene group are The alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may have a fluorine atom as a substituent, a fluorine atom or a cyano group may be substituted, R ₂ is a single bond, carbon An alkylene group having a number of 1 to 3, an oxygen atom, a sulfur atom, —CH═CH—, —NH—, or —COO—, a is an integer of 0 to 3, and when a is 2 or more, R ₁ And R ₂ may be the same or different, R ₃ is a fluorine atom or a cyano group, and b is an integer of 0 to 4.
In the formula (2), R ₄ is a phenylene group or a cyclohexylene group, and part or all of the hydrogen atoms of the phenylene group or cyclohexylene group are a linear or cyclic alkyl group having 1 to 10 carbon atoms, It may be substituted with a linear or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group. R ₅ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom, or —NH—. c is an integer of 1 to 3, and when c is 2 or more, R ₄ and R ₅ may be the same or different. R ₆ is a fluorine atom or a cyano group, and d is an integer of 0 to 4. R ₇ is an oxygen atom, —COO— * or —OCO— * (in the above, a bond marked with “*” is bonded to R ₈ ). R ₈ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group. R ₉ is a single bond, —OCO— (CH ₂ ) _f — * or —O (CH ₂ ) _g — * (provided that a bond marked with “*” above binds to a carboxyl group). f and g are each an integer of 1 to 10, and e is an integer of 0 to 3. ) [A] A polyorganosiloxane compound having a photo-alignment group is
At least one selected from the group consisting of a polyorganosiloxane having an epoxy group, a hydrolyzate thereof and a condensate of the hydrolyzate;
The composition for aligning organic semiconductors according to claim 1 , which is a reaction product of at least one selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2). . The epoxy group is a compound represented by the following formula _(X 1 -1) or _(X 1 -2) organic semiconductor oriented composition according to claim 2 represented by.

(In the formula (X ₁ -1), A is an oxygen atom or a single bond. H is an integer of 1 to 3, i is an integer of 0 to 6. However, when i is 0, A is It is a single bond.
Wherein _(X 1 -2), j is an integer from 1 to 6.
In the formulas (X ₁ -1) and (X ₁ -2), “*” represents a bond. ) [B] at least one structure selected from the group consisting of an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a t-butyl ester structure of a carboxylic acid. The composition for organic-semiconductor alignment of any one of Claims 1-3 which further contains the compound which has one or more. The organic-semiconductor alignment film formed with the composition for organic-semiconductor alignment of any one of Claims 1-4 . A gate electrode formed on the substrate;
An insulating film formed to cover the gate electrode;
The organic semiconductor alignment film according to claim 5 formed on the insulating film,
A source electrode and a drain electrode formed on the organic semiconductor alignment film;
An organic semiconductor element having at least an organic semiconductor layer formed between the source electrode and the drain electrode. An insulating film forming step of forming an insulating film so as to cover the gate electrode formed on the substrate;
A coating film forming step of forming a coating film on the insulating film from the organic semiconductor alignment composition according to any one of claims 1 to 4 ,
An electrode forming step of forming a source electrode and a drain electrode on the 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, the manufacturing method of the organic-semiconductor element which further has the process of irradiating the said coating film with linearly polarized light, and forming an organic-semiconductor alignment film.

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