TWI475075B - Organic semiconductor alignment composition, organic semiconductor alignment film, organic semiconductor element, and method of manufacturing the same - Google Patents

Description

Organic semiconductor alignment composition, organic semiconductor alignment film, organic semiconductor element, and method of manufacturing the same

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

In recent years, liquid crystal display elements have advantages such as low power consumption, ease of miniaturization, and flatness, and are therefore suitable for use in a wide range of applications from small liquid crystal display devices such as mobile phones to large-screen liquid crystal display devices such as liquid crystal televisions. In such a liquid crystal display device, an image can be displayed by switching the liquid crystals assigned to the respective points to ON/OFF, and a thin film transistor (TFT) is used for ON/OFF switching of the liquid crystal.

As a semiconductor device typified by a field effect type TFT, an inorganic semiconductor such as germanium is widely used, and an organic semiconductor is gradually developed. The organic semiconductor includes a low molecular organic semiconductor and a high molecular organic semiconductor, and a low molecular organic semiconductor which is widely used for constituting such a material is a pentacene or a polymer organic semiconductor which is a polythiophene derivative. In the low molecular organic semiconductor, a semiconductor layer is formed by a vapor deposition method. On the other hand, the polymer organic semiconductor can form a semiconductor layer by a coating method (such as spin coating, inkjet method, or printing method) without using a vacuum or a high temperature process. Rather, it can be coated at room temperature in the atmosphere, so it has the advantage of being able to be manufactured at low cost. Further, since it is expected to be formed on a resin substrate, it is expected to be applied to various fields such as flexible displays, electronic papers, plastic IC cards, organic ELs, and solar cells in addition to TFTs.

In order to achieve high performance of an organic semiconductor, for example, a high operating frequency (for example, several hundred kHz) and a high ON current/OFF current ratio (ON/OFF ratio) are required for a switching TFT. For example, 10 ⁴ to 10 ⁶ about). In order to exhibit such a function, it is effective to control the drain current between the source and the drain. Here, the drain current (Id) of the saturated region satisfies the following relation (I).

Id=(W/2L)μCi(Vg-Vt) ² ‧‧‧(I)

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

Therefore, in order to satisfy the above requirements, W/2L and Ci can be increased, but if the former W/2L is increased, it is necessary to form a highly precise electrode pattern, resulting in a cost increase. On the other hand, when the latter Ci is increased, the electrical conductivity of the gate insulating film is increased, and the film thickness must be made thin, and there is a great limitation from the viewpoint of preventing defects such as pores from occurring in a large-area process. Therefore, a method of increasing the mobility μ of the carrier with a small restriction is being developed. As a specific method for increasing the carrier mobility μ, it is attempted to introduce organic semiconductor molecules in a predetermined direction by introducing an alignment film defining an alignment of organic semiconductor molecules, thereby increasing the overlap of π orbitals (π electrons) contributing to electrical conduction. , improve the mobility of the carrier.

The relationship between the overlap of the π orbitals caused by the alignment of the organic semiconductor molecules and the movement of the carriers can be considered as the following reason. In the π-electron conjugated polymer constituting the polymer-based organic semiconductor, the organic semiconductor polymer chain is aligned in the same direction (direction between the electrodes) as the alignment direction of the alignment film, and may be aligned in the direction of the main chain. The carrier moves. Further, in the low molecular organic semiconductor, since π stacking of the organic semiconductor molecules is formed in a direction perpendicular to the alignment direction of the alignment film (direction between the electrodes), it is possible to carry the π orbits in the direction in which they overlap. Sub-movement.

Although the alignment of the organic semiconductor molecules includes a method of rubbing the organic semiconductor layer in the direction in which the carrier moves, and improving the anisotropy, it is not possible to satisfy the rule that the π orbital plane overlaps, and there is a possibility of causing frictional damage or contamination. In order to solve the problem of this friction method, a non-contact optical alignment method has been developed. As an organic transistor using the photo-alignment method, for example, in Japanese Laid-Open Patent Publication No. 2009-289783, in the embodiment, it is proposed to sequentially form a substrate, a gate, a gate insulating layer, an alignment layer, a source, and a drain. And an organic field effect type transistor having an organic semiconductor layer of a specific material.

However, although the organic transistor of the above document can obtain a certain degree of carrier mobility, it is necessary to correspond to the amount of light irradiation of the alignment of the photoalignment group, and it is not considered that the sensitivity of the light alignment is sufficiently high. Further, when attempting to apply an organic semiconductor to various fields, it is necessary to have weather resistance (heat resistance) capable of maintaining the original carrier mobility at a high ratio even under severe use conditions such as high temperature. However, in the above documents, heat resistance (carrier mobility stability) required as an alignment layer in an organic semiconductor element is not considered at all.

According to this situation, it is desirable to start an organic semiconductor alignment film which has good light alignment sensitivity, has carrier mobility stability derived from high heat resistance, and can achieve high level of orientation by organic semiconductor molecules. The high carrier mobility caused by the alignment of the opposite sex; and the development of an organic semiconductor alignment composition capable of forming the organic semiconductor alignment film.

Prior technical literature

Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2009-289783

The present invention has been made in view of the above problems, and an object thereof is to provide an organic semiconductor alignment film which has good light alignment sensitivity, can realize carrier mobility stability derived from high heat resistance, and can exhibit an organic semiconductor. The molecule exhibits excellent carrier mobility with high level anisotropic alignment; and an organic semiconductor alignment composition capable of forming the organic semiconductor alignment film, an organic semiconductor element having the above organic semiconductor alignment film, and the organic semiconductor element Manufacturing method.

The invention proposed to solve the above problems is an organic semiconductor alignment composition comprising [A] a polyorganosiloxane compound having a photo-alignment group.

Since the organic semiconductor alignment composition contains [A] a polyorganosiloxane compound having a photo-alignment group, when an organic semiconductor alignment film is formed using the same, the photo-alignment group can be lowered due to good light alignment sensitivity. The amount of light irradiation necessary for the grouping is adjusted, whereby the production efficiency of the organic semiconductor element can be improved. Further, in the organic semiconductor alignment film formed using the organic semiconductor alignment composition, the organic semiconductor molecule can be at a high level by an anisotropically aligned [A] polyorganosiloxane compound having a photo-alignment group. Anisotropic alignment, whereby excellent carrier mobility can be achieved in an organic semiconductor device. Further, the polyorganosiloxane compound having a photo-alignment group of [A] of the organic semiconductor alignment composition has thermal stability and chemical stability of the obtained alignment film by using polyorganosiloxane as a main chain. It is high and exhibits high heat resistance, whereby the original carrier mobility can be maintained for a long time and at a high ratio even after being heated.

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-alignment group, high anisotropy can be imparted to the alignment of the organic semiconductor molecules by the obtained organic semiconductor alignment film, and further Improve the mobility of the carrier of the organic semiconductor.

In the organic semiconductor alignment composition, the group having a cinnamic acid structure is preferably a group composed of a group derived from a compound represented by the following formula (1) and a group derived from the compound represented by (2). At least one selected from the group (hereinafter, one or both of the compounds represented by the following formula (1) and the compound represented by the following formula (2) are simply referred to as "specific cinnamic acid derivatives").

In the formula (1), R ₁ is a part of a hydrogen atom extending a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group, and a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group. Alternatively, all of them may be substituted by 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.

In the formula (2), R ₄ is a phenyl group or a cyclohexyl group, and a part or the whole of the hydrogen atom of the phenyl group or the cyclohexyl group may be a chain or cyclic alkyl group having 1 to 10 carbon atoms. And a chain or cyclic alkoxy group having a carbon number of 1 to 10, 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-* (wherein, in the above, a "*" linkage and a R ₈ linkage). R ₈ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group. R ₉ is a single bond, -OCO-(CH ₂ ) _f- * or -O(CH ₂ ) _g- * (wherein, in the above, a "*" linkage and a carboxyl linkage are attached. f and g are 1 respectively An integer of ~10, where e is an integer from 0 to 3.)

By using the group derived from the above specific cinnamic acid derivative as the above-mentioned group having a cinnamic acid structure, the anisotropic property imparted to the organic semiconductor molecule, that is, the alignment property, and the π electron of the organic semiconductor molecule can be easily fixed. The conjugate or stacking further increases the carrier mobility of the organic semiconductor layer.

In the organic semiconductor alignment composition, [A] the polyorganosiloxane compound having a photo-alignment group is preferably a condensation of a polyorganosiloxane having an epoxy group, a hydrolyzate thereof and a hydrolyzate thereof. 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 organic semiconductor alignment composition, by using a reactivity between a polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative, it is possible to introduce a photoalignment from a polyorganosiloxane as a main chain. a side chain group of a specific cinnamic acid derivative.

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 from 1 to 3, and i is an integer from 0 to 6. Wherein, when i is 0, A is a single bond.

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

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

By using the epoxy group represented by the above formula (X ₁ -1) or (X ₁ -2) as the above epoxy group, it can be easily introduced from the polyorganosiloxane of the organic semiconductor alignment composition. a side chain group of a particular cinnamic acid derivative.

The organic semiconductor alignment composition preferably further contains [B] a acetal ester structure having two or more carboxylic acids, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, and a carboxy group. A compound of at least one structure selected from the group consisting of acid tertiary butyl ester structures. The composition for organic semiconductor alignment is passed through a compound containing such a component [B] (hereinafter, simply referred to as "compound having an ester structure"), and in a sintering step after exposure (hereinafter referred to as "post-baking"), By generating an acid, crosslinking of the polyorganosiloxane compound having a photo-alignment group can be promoted by the generated acid, thereby improving the heat resistance of the obtained organic semiconductor alignment film.

The organic semiconductor alignment composition preferably further contains at least one polymer selected from the group consisting of polyacrylic acid and polyamidiamine.

The organic semiconductor alignment composition can exhibit a high concentration by using at least one polymer selected from the group consisting of poly(prolyl) and polyamidiamine [C]. Insulation. Further, the formed organic semiconductor alignment film has a polyorganosiloxane compound having a photo-alignment group which contributes to the anisotropic alignment of the organic semiconductor molecules, and is present in the vicinity of the surface of the alignment film. The alignment group, the organic semiconductor molecule can be anisotropically aligned at a high level, so that excellent carrier mobility can be achieved in the organic semiconductor element.

In the organic semiconductor alignment composition, the polyamic acid and the polyimine are preferably composed of an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. A reaction product of at least one tetracarboxylic dianhydride selected from the group and at least one diamine selected from the group consisting of aliphatic diamines, alicyclic diamines, and aromatic diamines. When the above polyamic acid and polyimine are polymers obtained from such a monomer, the electrical properties represented by the insulating properties of the obtained organic semiconductor alignment film can be further improved.

The organic semiconductor alignment film of the present invention is formed of the organic semiconductor alignment composition. As a result, even if the organic semiconductor alignment film is heated, it exhibits excellent carrier mobility stability due to high heat resistance, and at the same time, easily defines the π-electron conjugate plane or π of the organic semiconductor molecule due to the photo-alignment group. By stacking alignment, excellent carrier mobility can be found in the organic semiconductor layer. Further, when the organic semiconductor alignment composition contains at least one polymer selected from the group consisting of polyglycine and polyimine, the organic semiconductor alignment film can exhibit high insulation.

The organic semiconductor alignment film of the present invention preferably has a group having a cinnamic acid structure in a range from 30% to 30% of the film thickness. The group having a cinnamic acid structure which contributes to the alignment of the organic semiconductor can more effectively induce the alignment of the organic semiconductor molecules by being in the vicinity of the surface of the organic semiconductor side of the alignment film in the above range.

The organic semiconductor device of the present invention includes a gate electrode formed on a substrate, an insulating film formed over the gate electrode, and an organic semiconductor alignment film formed on the insulating film by the organic semiconductor alignment composition, in the organic semiconductor alignment film a source and a drain formed thereon, and an organic semiconductor layer formed at least between the source and the drain. In the organic semiconductor device, the alignment film formed of the organic semiconductor alignment composition is used as an alignment film for an organic semiconductor, so that excellent optical alignment sensitivity can be exhibited, the amount of light irradiation can be reduced, and the load in the organic semiconductor layer can be improved. Sub mobility. Thereby, a high operating frequency and a high ON/OFF ratio can be realized in the organic semiconductor element. Further, since the alignment film formed of the organic semiconductor alignment composition has high heat resistance, the original carrier mobility can be maintained for a long period of time even after being heated.

The method for producing an organic semiconductor device of the present invention includes the step of forming an insulating film to cover an insulating film formed on the substrate, and forming a coating film on the insulating film by forming a coating film on the organic semiconductor alignment composition An electrode forming step of forming a source and a drain on the coating film; and an organic semiconductor layer forming step of forming an organic semiconductor layer between the source and the drain; and further before the step of forming the organic semiconductor layer There is a step of irradiating the coating film with linearly polarized light to form an organic semiconductor alignment film. By using the manufacturing method of the semiconductor element, the organic semiconductor element can be efficiently and simply manufactured.

The organic semiconductor device of the present invention includes a gate electrode formed on a substrate, and an organic semiconductor alignment film for covering the gate electrode formed of the organic semiconductor alignment composition containing the [C] component, on the organic semiconductor alignment film A source and a drain are formed, and an organic semiconductor layer is formed at least between the source and the drain. In the organic semiconductor device, an alignment film formed of the organic semiconductor alignment composition containing the [C] component is used as a so-called gate insulating film, so that excellent insulating properties can be exhibited and the organic semiconductor layer can be improved. The carrier mobility makes it possible to achieve a high operating frequency and a high ON/OFF ratio in the organic semiconductor element.

The method for producing an organic semiconductor device of the present invention includes a coating film forming step of forming a coating film by using the organic semiconductor alignment composition to cover a gate electrode formed on the substrate, and 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 between the source and the drain; and further comprising the step of irradiating the coating film with linearly polarized light to form an organic semiconductor alignment film before the step of forming the organic semiconductor layer . By using the manufacturing method of the semiconductor element, the organic semiconductor element can be efficiently and simply manufactured.

As described above, the organic semiconductor alignment composition, the organic semiconductor alignment film, the organic semiconductor device, and the method for producing the same of the present invention have good sensitivity in light alignment, and can achieve carrier mobility stability through high heat resistance, and can also be organic. The semiconductor molecules are anisotropically aligned at a high level, and exhibit excellent carrier mobility.

Type of implementation of the invention

Since the organic semiconductor alignment composition of the present invention contains [A] a polyorganosiloxane compound having a photo-alignment group (hereinafter, simply referred to as "photo-aligned polyorganosiloxane compound"), it can be made high by Sensitivity to the optical alignment, reducing the amount of light necessary for alignment. In addition, since the organic semiconductor alignment film is used, the obtained organic semiconductor alignment film exhibits high heat resistance, whereby high carrier mobility stability after heating can be exhibited, and the organic semiconductor alignment film is excellent. Since the optical alignment is excellent, an anisotropic alignment at a high level can be exhibited in the organic semiconductor layer.

The organic semiconductor alignment composition may contain a [B] ester-containing structural compound as a suitable component, and/or [C] from poly-proline, while containing the [A] photo-aligned polyorganosiloxane compound. At least one polymer selected from the group consisting of polyimine and, in addition, as a optional component, a polymer other than the photo-aligned polyorganosiloxane compound (hereinafter referred to as "other polymer") may be further contained. a curing agent, a curing catalyst, a curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, a surfactant, a photosensitizing compound, etc. . Hereinafter, the composition for organic semiconductor alignment will be described.

<[A] component: polyorganosiloxane compound having a photo-alignment group>

For the polyorganosiloxane compound having a photo-alignment group, [A] is selected from the group consisting of a polycondensate of a polyorganosiloxane, a hydrolyzate thereof, and a hydrolyzate thereof as a main chain. On at least one of the portions, a photo-alignment group is introduced as a side chain. When the organic semiconductor alignment film is formed using the organic semiconductor alignment composition, when the photo-alignment group is irradiated with anisotropic light such as polarized light, the rearrangement of the molecules is induced in the organic semiconductor alignment film. An anisotropic chemical reaction, etc. Anisotropy can be imparted to the organic semiconductor molecules by the molecular structure change of the alignment film having the anisotropy. Further, due to the photo-alignment group and the polyorganosiloxane compound, the sensitivity of light alignment is good, and a low amount of light irradiation can be achieved. At the same time, since the polyorganosiloxane is used as the main chain, the organic semiconductor alignment film formed of the semiconductor alignment composition has excellent chemical stability and thermal stability, and exhibits high heat resistance, so even after being heated It is also possible to maintain the carrier mobility for a long time.

(photoalignment group)

As described above, the photo-alignment group induces a change in the microstructure of the molecules constituting the alignment film via irradiation with anisotropic light. The photo-alignment group is not particularly limited, and a group derived from various compounds exhibiting photo-alignment properties can be used. The mechanism which exhibits anisotropy as a photo-alignment group is classified into two types, a photoreactive type and a photoisomerization type. The photoreactive type is further classified into a dimeric type, a decomposed type, a combined type, and a decomposed crosslinked type. From the viewpoint of not contaminating the organic semiconductor layer, it is preferred that the type of impurity ions, radicals, or the like does not remain after the light irradiation, and therefore it is preferably a photoisomerization type or a dimerization type.

Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, and a cinnamic acid-containing group containing cinnamic acid or a derivative thereof as a basic skeleton. a benzophenone-containing group containing phenylacryl benzene or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, having coumarin The coumarin-containing group having a basic skeleton or a derivative thereof, a polyimine-containing structure containing a polyimine or a derivative thereof as a basic skeleton, and the like. Among these photo-alignment groups, in view of exhibiting dimerization-type anisotropy and facilitating introduction of high alignment energy, a group having a cinnamic acid structure containing cinnamic acid or a derivative thereof as a basic skeleton is preferable. Further, cinnamic acid or a derivative thereof can be dimerized by light irradiation, and is not limited to cis or trans.

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, and is preferably a compound represented by the above formula (1) and a compound represented by the above formula (2). a group of at least one of a compound (that is, a specific cinnamic acid derivative). Further, in the above formula (1), R ₁ is a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group, and the hydrogen group is a phenyl group, a biphenyl group, a terphenyl group or a hydrogen group. A part or all of the atom may be substituted by 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.

The compound represented by the above formula (1) may, for example, be the following.

Among these, R _{1 is} preferably an unsubstituted phenyl group or a phenyl group which may be substituted by a fluorine atom or an alkyl group having 1 to 3 carbon atoms, and R _{2 is} preferably a single bond or an oxygen atom. Or -CH ₂ =CH ₂ -. b is preferably 0 to 1, and when a is 1 to 3, b is particularly preferably 0.

In the above formula (2), R ₄ is a phenyl or cyclohexyl group, and a part or the whole of the hydrogen atom of the phenyl or cyclohexyl group may be a chain or cyclic alkane having 1 to 10 carbon atoms. The group has a chain or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group. R ₅ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-. c is an integer of 1 to 3, and when c is 2 or more, R ₄ and R ₅ may be the same or different. R ₆ is a fluorine atom or a cyano group, and d is an integer of 0 to 4. R ₇ is an oxygen atom, -COO-* or -OCO-* (wherein, in the above, a "*" linkage and a R ₈ linkage). R ₈ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group. R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -* (wherein, in the above, a "*" linkage and a carboxyl linkage are attached. f and g are 1 respectively An integer of ~10, where e is an integer from 0 to 3.

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

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

(Synthesis of specific cinnamic acid derivatives)

The synthesis step of the specific cinnamic acid derivative is not particularly limited, and it can be carried out by a combination of a conventionally known method. As a typical synthesis step, for example, (1) a compound having a benzene ring skeleton substituted with a halogen atom and acrylic acid can be exemplified under basic conditions, and reacted in the presence of a transition metal catalyst to obtain a specific cinnamic acid derivative. a method; (2) a cinnamic acid in which a hydrogen atom of a benzene ring is substituted by a halogen atom and a compound having a benzene ring skeleton substituted by a halogen atom under basic conditions, reacting in the presence of a transition metal catalyst to form a specific cinnamic acid Derivative methods, etc. However, the synthetic step of the specific cinnamic acid derivative is not limited to these methods.

(a portion derived from at least one selected from the group consisting of a polyorganosiloxane, a hydrolyzate thereof, and a hydrolyzate thereof)

a portion selected from the group consisting of a condensate of a polyorganosiloxane, a hydrolyzate thereof, and a hydrolyzate thereof as a main chain in the [A] photo-aligned polyorganosiloxane compound, There is no particular limitation as long as it has a structure derived from a structure capable of introducing the above photo-alignment group itself. [A] a photo-alignment polyorganosiloxane compound comprising such a portion derived from at least one selected from the group consisting of a polyorganosiloxane, a hydrolyzate thereof and a hydrolyzate thereof, and the light from the above-mentioned display A group of an ortho-compounding compound.

Examples of the structure capable of introducing the photo-alignment group include a hydroxyl group, an epoxy group, an amine group, a carboxyl group, a thiol group, an ester group, and a decylamino group. Among them, an epoxy group is preferred in view of ease of introduction and preparation.

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

(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 it introduces an epoxy group as a side chain in the polyorganosiloxane. The polyorganosiloxane having the epoxy group is preferably a group consisting of a polyorganosiloxane having a repeating unit represented by the following formula (3), a hydrolyzate thereof, and a condensate of the hydrolyzate thereof. At least one of the selected ones.

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, an alkyl group having 1 to 20 carbon atoms or a carbon atom. The number is 6 to 20 aryl groups.

Further, the hydrolysis condensate of the polyorganosiloxane having the repeating unit represented by the above formula (3) is not only a hydrolysis condensate between the polyorganosiloxanes but also contains the above formula (3). Hydrolysis condensate in the case where the polyorganosiloxane having the main chain is branched and crosslinked, and the polyorganosiloxane having the repeating unit represented by the above formula (3) is hydrolyzed and condensed to form a polyorganosiloxane. the concept of.

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 glycidyl group, a glycidoxy group, and an epoxycyclohexyl group. . This X ₁ corresponds to the epoxy group of the above polyorganosiloxane having an epoxy group. The above epoxy group (that is, X ₁ ) is preferably represented by the above formula (X ₁ -1) or (X ₁ -2), and further, in the above formula (X ₁ -1) or (X ₁ -2) Among the epoxy groups shown, a group represented by the following formula (X ₁ -1-1) or (X ₁ -2-1) is preferred.

In the above formula, "*" indicates a connection key.

In the Y ₁ in the above formula (3), the alkoxy group having 1 to 10 carbon atoms may, for example, be a methoxy group or an ethoxy group, or an alkane having 1 to 20 carbon atoms. Examples of the group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-decyl group, n-lauric group, and n-dome. Alkyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and the like.

The polyorganosiloxane having an epoxy group is preferably a polystyrene-converted mass average molecular weight measured by gel permeation chromatography (GPC) of from 500 to 100,000, more preferably from 1,000 to 10,000, still more preferably 1,000. ~5,000.

The polyorganosiloxane having an epoxy group is preferably a mixture of a decane compound having an epoxy group or a decane compound having an epoxy group and another decane compound, preferably in a suitable organic solvent. In the presence of water and a catalyst, it is synthesized by hydrolysis or hydrolysis or condensation.

Examples of the above decane compound having an epoxy group include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl group. Dimethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl dimethyl methoxy decane, 3-glycidoxy propyl dimethyl Ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like.

The other decane compound may, for example, be tetrachlorosilane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, or the like. Butoxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, triisopropoxy decane, tri-n-butoxy decane, tri- or 2-butoxy decane, Fluorine trichlorodecane, fluorotrimethoxydecane, fluorotriethoxydecane, fluorotri-n-propoxy decane, fluorotriisopropoxy decane, fluorotri-n-butoxy decane, fluorotri-l-butoxy Decane, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane, Methyl tri- or 2-butoxybutane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)ethyl Triethoxydecane, 2-(trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltriisopropoxydecane, 2-(trifluoromethyl)ethyl Tri-n-butoxy Alkane, 2-(trifluoromethyl)ethyltri- or 2-butoxybutane, 2-(perfluoro-n-hexyl)ethyltrichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethoxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-hexyl)ethyltriisopropoxydecane, 2-(Perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyltri- or 2-butoxybutane, 2-(perfluoro-n-octyl)ethyltrichloromethane , 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-propoxy Decane, 2-(perfluoro-n-octyl)ethyltriisopropoxydecane, 2-(perfluoro-n-octyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-octyl)ethyltri - 2 - butyl decane, hydroxymethyl trichloro decane, hydroxymethyl trimethoxy decane, hydroxyethyl trimethoxy decane, hydroxymethyl tri-n-propoxy decane, hydroxymethyl triisopropoxy decane , hydroxymethyl tri-n-butoxy decane, hydroxymethyl tri- or 2-butoxy decane, 3-(methyl) propylene methoxy propyl trichloride Decane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)acryloxypropyltricarboxylate N-propoxy decane, 3-(meth) propylene methoxypropyl triisopropoxy decane, 3-(methyl) propylene methoxy propyl tri-n-butoxy decane, 3-(methyl) Propylene methoxypropyl tri- or 2-butoxybutane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyl Tri-n-propoxy decane, 3-mercaptopropyltriisopropoxy decane, 3-mercaptopropyltri-n-butoxy decane, 3-mercaptopropyltri-di-butoxy decane, decylmethyltrimethoxy Base decane, decylmethyltriethoxy decane, vinyl trichloro decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane , vinyl tri-n-butoxy decane, vinyl tri- or 2-butoxy decane, allyl trichloro decane, allyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-butyl Propoxy decane Triisopropoxy decane, allyl tri-n-butoxy decane, allyl tri- or 2-butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane , phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, phenyl tri-n-butoxy decane, phenyl tri- or 2-butoxy decane, methyl dichloro decane, methyl dimethoxy Base decane, methyl diethoxy decane, methyl di-n-propoxy decane, methyl diisopropoxy decane, methyl di-n-butoxy decane, methyl di- or 2-butoxy decane, Methyl dichlorodecane, dimethyl dimethoxy decane, dimethyl diethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butyl Oxydecane, dimethyl di-secondary butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl) Ethyl]dimethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl] Di-n-propoxy decane, (methyl) [2-(perfluoro-n-octyl)ethyl]diisopropoxy decane, (A [2-(perfluoro-n-octyl)ethyl]di-n-butoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-butoxybutane, (a) (3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl)(3-mercaptopropyl)diethoxydecane, (methyl) (3-mercaptopropyl)di-n-propoxyoxydecane, (methyl)(3-mercaptopropyl)diisopropoxydecane, (methyl)(3-mercaptopropyl)di-n-butoxydecane , (methyl) (3-mercaptopropyl) di- or 2-butoxybutane, (methyl) (vinyl) dichlorodecane, (methyl) (vinyl) dimethoxy decane, (methyl ) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy decane, (methyl) (vinyl) diisopropoxy decane, (methyl) (vinyl) two n-Butoxydecane, (methyl) (vinyl) di- or 2-butoxy decane, divinyl dichloro decane, divinyl dimethoxy decane, divinyl diethoxy decane, diethylene Di-n-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane, divinyl di-di-butoxy decane, diphenyl dichloro decane, Phenyldimethoxydecane, diphenyldiethoxydecane, diphenyldi-n-propoxydecane, diphenyldiisopropoxydecane, diphenyldi-n-butoxydecane, diphenyl Di-secondary butoxy decane, chlorodimethyl decane, methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, trimethyl decane bromide, trimethyl decane iodide , methoxy trimethyl decane, ethoxy trimethyl decane, n-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, secondary butoxy three Methyl decane, tertiary butoxy trimethyl decane, (chloro) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) a monodecane atom such as methyl decane, (chloro) (methyl) diphenyl decane, (methoxy) (methyl) diphenyl decane, (ethoxy) (methyl) diphenyl decane The decane compound, and the product name, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844 , X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-17 0B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X- 40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR- 213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.); Glass Resin (Stock) manufacturing); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, manufactured by Toray-Dow Corning Co., Ltd.); FZ3711, FZ3722 (above, Unicar, Japan) One (stock) manufacturing); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45 , DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, manufactured by Chisso); Methyl silicate MS51, Methyl silicate MS56 (above, Mitsubishi) (Unit) manufactured); Ethyl silicate28, Ethyl silicate 40, Ethyl silicate 48 (above, by Colcoat (shares) manufactured); GR100, GR650, GR908, GR950 (by Showa Denko (shares)) and the like partial condensate.

Among these other decane compounds, from the viewpoint of the alignment property and chemical stability of the obtained organic semiconductor alignment film, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, and methyl three are preferable. Ethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-mercapto Propyltriethoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane.

The polyorganosiloxane having an epoxy group used in the present invention has an epoxy equivalent in order to introduce a sufficient amount of a side chain having photo-alignment properties while suppressing an undesirable side reaction caused by an excessive amount of introduction of an epoxy group. It is preferably from 100 to 10,000 g/mol, more preferably from 150 to 1,000 g/mol. Therefore, it is preferred to set the use ratio of the decane compound having an epoxy group and the other decane compound when synthesizing the polyorganosiloxane having an epoxy group, so that the epoxy equivalent of the obtained polyorganosiloxane is range.

Specifically, the other decane compound is preferably used in an amount of from 0 to 50% by mass, more preferably from 5 to 30% by mass, based on the total amount of the polyorganosiloxane having an epoxy group and other decane compounds.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane having an epoxy group include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

Examples of the hydrocarbon include, for example, toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexane. a ketone or the like; examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, 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, and An alkane or the like; as the above-mentioned alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among these, it is preferably water-insoluble. These organic solvents may be used singly or in combination of two or more.

The organic solvent is preferably used in an amount of 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the total of the decane compound. Further, when the polyorganosiloxane having an epoxy group is produced, the amount of water is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles per mole of the total decane compound.

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

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

As the above-mentioned organic base, for example, ethylamine, diethylamine or piperazine can be exemplified. Primary or secondary organic amines such as piperidine, pyrrolidine, pyrrole; like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo A tertiary organic amine such as undecene; a quaternary organic amine such as tetramethylammonium hydroxide. Among these organic bases, organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and the like are preferable in view of stable reaction. An organic quaternary ammonium salt such as tetramethylammonium oxide.

As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, it is possible to obtain a desired polyorganosiloxane with high hydrolysis and condensation rate without causing side reactions such as ring opening of an epoxy group, and thus it is excellent in production stability. Preferably. Further, the organic semiconductor alignment composition of the present invention containing a reaction product of an epoxy group-containing polyorganosiloxane and a specific cinnamic acid derivative, wherein the polyorganosiloxane is synthesized using an alkali metal compound or an organic base as a catalyst, It is suitable because it has excellent storage stability.

The reason is as pointed out in Chemical Reviews, Vol. 95, p. 1409 (1995). It is presumed that if an alkali metal compound or an organic base is used as a catalyst in the hydrolysis or condensation reaction, a random structure, a ladder structure or a cage is formed. The structure is such that a polyorganosiloxane having a small proportion of stanol groups cannot be obtained. In the case where the content of the stanol group is small, the condensation reaction between the stanol groups is suppressed, and when the organic semiconductor alignment composition of the present invention contains another polymer to be described later, the stanol group and other polymers are inhibited. The condensation reaction results in excellent storage stability.

As the catalyst, an organic base is particularly preferred. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions such as the temperature, and the like, and can be appropriately set. The specific amount of the organic base to be used is, for example, preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole, relative to the total of the decane compound.

Hydrolysis or hydrolysis, condensation reaction in the production of a polyorganosiloxane having an epoxy group, preferably by dissolving a decane compound having an epoxy group and other decane compounds used as needed in an organic solvent, The organic base is mixed with water and heated by, for example, an oil bath.

In the hydrolysis and condensation reaction, the heating temperature of the oil bath is desirably 130 ° C or less, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. When heating, the mixture may be stirred or left to stand under reflux.

After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. In the washing, in terms of easy washing operation, it is preferably washed with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by mass. The aqueous layer after washing is neutralized, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to obtain a desired polyorganosiloxane having an epoxy group.

In the present invention, commercially available ones can be used as the polyorganosiloxane having an epoxy group. Examples of such a product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, Chisso).

[A] Photo-aligned polyorganosiloxane compound comprising a portion derived from a hydrolyzate formed by hydrolysis of a polyorganosiloxane having an epoxy group itself, and a hydrolytic condensation formed from a polyorganosiloxane having an epoxy group; A portion of the hydrolysis condensate. These hydrolyzates or hydrolysis condensates which are constituent materials of the moieties are also prepared in the same manner as the hydrolysis and condensation conditions of the polyorganosiloxane having an epoxy group.

([A] Synthesis of polyorganosiloxane compounds having photo-alignment groups)

[A] A polyorganosiloxane compound having a photo-alignment group used in the present invention, for example, by a polyorganosiloxane having an epoxy group as described above and the above formula (1) and/or ( 2) The compound shown (i.e., a specific cinnamic acid derivative) is preferably synthesized by reaction in the presence of a catalyst.

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

As the catalyst, a known compound such as an organic base or a so-called curing accelerator which promotes the reaction of an epoxy compound and an acid anhydride can be used.

Examples of the above organic base include, for example, ethylamine, diethylamine, and piperazine. Primary or secondary organic amines such as piperidine, pyrrolidine, pyrrole; like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo An organic tertiary amine such as undecene; an organic quaternary ammonium such as tetramethylammonium hydroxide.

Among these organic bases, preferred are organic tertiary amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; such as tetramethylammonium hydroxide Organic quaternary ammonium salt.

The curing accelerator may, for example, be a tertiary amine such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine. Like 2-methylimidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2- Ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyano) Ethyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium Benzoate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole Anthracene trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-three 2,4-Diamino-6-(2'-n-undecylimidazolyl)ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-three , an isocyanuric acid addition product of 2-methylimidazole, an isocyanuric acid addition product of 2-phenylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1' )]Ethyl-s-three Imidazole compound such as isocyanuric acid adduct; organic phosphorus compound such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; like benzyltriphenylphosphonium chloride, tetra-n-butyl bromide Base, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyl three Phenyl hydrazine acetate, tetra-n-butyl fluorene O, O-diethyl phosphine dithiosulfate, tetra-n-butyl benzotriazole salt, tetraphenylphosphonium tetraphenyl borate, tetra-n-butyl a quaternary phosphonium salt such as tetrafluoroborate or tetra-n-butylphosphonium tetraphenylborate; like 1,8-diazobicyclo[5.4.0]undecene-7 and its organic acid salt Diazobiscycloalkenes; organometallic compounds such as zinc octoate, tin octoate, acetamidine aluminum complex; like tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride a quaternary ammonium salt such as tetra-n-butylammonium chloride; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or tin chloride; dicyanoquinone Amines and amines and epoxies a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator such as a fat addition product; a microcapsule type potential formed by covering a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound, or a quaternary phosphonium salt with a polymer A curing accelerator; an amine salt type latent curing accelerator; a latent curing accelerator such as a high temperature decomposing thermal cationic polymerization type latent curing accelerator such as a Lewis acid salt or a Bronsted acid salt.

Among these catalysts, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred.

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

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

[A] The photo-aligned polyorganosiloxane compound can be synthesized in the presence of an organic solvent as needed. Examples of the organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, and an alcohol compound. Among these, an ether compound, an ester compound, and a ketone compound are preferable from the viewpoints of solubility of a raw material and a product, and easiness of product purification. The concentration of the solid content of the solvent (the ratio of the mass of the component other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 50% by mass or less. The following quantities are used.

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

The above [A] photoalignment polyorganosiloxane compound is subjected to ring-opening addition of an epoxy group to a carboxyl group of a specific cinnamic acid derivative, and is introduced into a polyorganosiloxane having an epoxy group from a specific cinnamic acid. The structure of the derivative. This production method is simple, and is particularly suitable for increasing the introduction rate of a structure derived from a specific cinnamic acid derivative.

In the present invention, a part of the specific cinnamic derivative described above may be substituted with a compound represented by the following formula (4) within a range not impairing the effects of the present invention. In this case, the synthesis of the [A] photo-aligned polyorganosiloxane compound can be carried out by using a polyorganosiloxane having an epoxy group with a specific cinnamic acid derivative and a compound represented by the following formula (4). The mixture is reacted.

R ₁₀ ─R ₁₁ ─R ₁₂ (4)

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 a fluoroalkoxy group having 4 to 21 carbon atoms as R _{11 .} It is preferably a single bond, 1,4-cyclohexylene or 1,4-phenylene, and R _{12 is} preferably a carboxyl group.

Preferable examples of the compound represented by the above formula (4) include a compound represented by any one of the following formulas (4-1) to (4-3).

The compound represented by the above formula (4) contributes to inactivation of the active site of the [A] photoalignment polyorganosiloxane compound, and improves the stability of the organic semiconductor alignment composition. In the present invention, when the compound represented by the above formula (4) is used together with a specific cinnamic acid derivative, the total use ratio of the specific cinnamic acid derivative and the compound represented by the above formula (4) is relative to 1 mol of the polyorganic compound. The epoxy group has a cyclooxy group of preferably 0.001 to 1.5 mol, more preferably 0.01 to 1 mol, still more preferably 0.05 to 0.9 mol. In this case, the compound represented by the above formula (4) is preferably used in an amount of 50 mol% or less, more preferably 25 mol% or less, based on the total amount of the specific cinnamic acid derivative. When the ratio of use of the compound represented by the above formula (4) exceeds 50 mol%, there is a concern that the alignment property in the organic semiconductor alignment film may be lowered.

<[B] component: compound containing ester structure>

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

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

In the 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, and an aromatic group having 6 to 10 carbon atoms. The group or the aralkyl group having 7 to 10 carbon atoms, and in the formula (B-2), n1 is an integer of 2 to 10.

Wherein R ₁₃ in the above formula (B-1) is: an alkyl group, preferably a methyl group; an alicyclic group, preferably a cyclohexyl group; and an aryl group, preferably a phenyl group; The aralkyl group is preferably a benzyl group; the alkyl group as R ₁₄ is preferably an alkyl group having 1 to 6 carbon atoms; and the alicyclic group is preferably an alicyclic ring having 6 to 10 carbon atoms. The aryl group is preferably a phenyl group; and the aralkyl group is preferably a benzyl group or a 2-phenylethyl group. As n1 in the formula (B-2), it is preferably 3 or 4.

The group represented by the above formula (B-1) includes, for example, 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, and 1 -isopropoxyethoxycarbonyl, 1-n-butoxyethoxycarbonyl, 1-isobutoxyethoxycarbonyl, 1-secondary butoxyethoxycarbonyl, 1-tertiary butoxy Ethyl ethoxycarbonyl, 1-cyclopentyloxyethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 1-low Ketoethoxycarbonyl, 1- Alkoxyethoxycarbonyl, 1-phenoxyethoxycarbonyl, 1-(1- Ethoxy)carbonyloxycarbonyl, 1-benzyloxyethoxycarbonyl, 1-phenylethyloxyethoxycarbonyl, (cyclohexyl)(methoxy)methoxycarbonyl, (cyclohexyl) (ethoxy)methoxycarbonyl, (cyclohexyl)(n-propoxy)methoxycarbonyl, (cyclohexyl)(isopropoxy)methoxycarbonyl, (cyclohexyl)(cyclohexyloxy) Methoxycarbonyl, (cyclohexyl)(phenoxy)methoxycarbonyl, (cyclohexyl)(benzyloxy)methoxycarbonyl, (phenyl)(methoxy)methoxycarbonyl, (benzene (ethoxy)methoxycarbonyl, (phenyl)(n-propoxy)methoxycarbonyl, (phenyl)(isopropoxy)methoxycarbonyl, (phenyl)(cyclohexyloxy) Methoxycarbonyl, (phenyl)(phenoxy)methoxycarbonyl, (phenyl)(benzyloxy)methoxycarbonyl, (benzyl)(methoxy)methoxycarbonyl, (benzyl)(ethoxy)methoxycarbonyl, (benzyl)(n-propoxy)methoxycarbonyl, (benzyl)(isopropoxy)methoxycarbonyl, (benzyl) (cyclo) Hexyloxy)methoxycarbonyl, (benzyl)(phenoxy)methoxycarbonyl, (benzyl)(benzyloxy)methoxycarbonyl, etc.; as represented by the above formula (B-2) Groups, for example, Among the 2-tetrahydrofuranyloxycarbonyl group, the 2-tetrahydropyranyloxycarbonyl group and the like, 1-ethoxyethoxycarbonyl group, 1-n-propoxyethoxycarbonyl group, 1- Cyclohexyloxyethoxycarbonyl, 2-tetrahydrofuranyloxycarbonyl, 2-tetrahydropyranyloxycarbonyl, and the like.

Examples of the ketal ester-containing group of the carboxylic acid include groups represented by the following formulas (B-3) to (B-5).

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 n 2 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.

In particular, the alkyl group as R ₁₅ in the above formula (B-3) is preferably a methyl group, and as R ₁₆ , each is preferably a methyl group; and the alicyclic group is preferably a cyclohexyl group. Preferably, the aryl group is a phenyl group; the aralkyl group is preferably a benzyl group; and for R ₁₇ , the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms; and the alicyclic group is Preferably, it is an alicyclic group having 6 to 10 carbon atoms; an aryl group is preferably a phenyl group; and an aralkyl group is preferably a benzyl group or a 2-phenylethyl group; The alkyl group of R ₁₈ in -4) is preferably a methyl group, and as n2 is preferably 3 or 4; the alkyl group as R ₁₉ in the formula (B-5) is preferably a methyl group, and as n3, it is preferably 3 or 4.

Each of the groups represented by the above formula (B-3) includes, for example, 1-methyl-1-methoxyethoxycarbonyl group, 1-methyl-1-ethoxyethoxycarbonyl group. , 1-methyl-1-n-propoxyethoxycarbonyl, 1-methyl-1-isopropoxyethoxycarbonyl, 1-methyl-1-n-butoxyethoxycarbonyl, 1 -Methyl-1-isobutoxyethoxycarbonyl, 1-methyl-1-dimethoxybutoxyethoxycarbonyl, 1-methyl-1-tris-butoxyethoxycarbonyl, 1 -methyl-1-cyclopentyloxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl, 1-methyl-1-nor Ketoethoxycarbonyl, 1-methyl-1- Ethoxyethoxycarbonyl, 1-methyl-1-phenoxyethoxycarbonyl, 1-methyl-1-(1-naphthyloxy)ethoxycarbonyl, 1-methyl-1- Benzyloxyethoxycarbonyl, 1-methyl-1-phenylethyloxyethoxycarbonyl, 1-cyclohexyl-1-methoxyethoxycarbonyl, 1-cyclohexyl-1-ethoxy Ethyloxycarbonyl, 1-cyclohexyl-1-n-propoxyethoxycarbonyl, 1-cyclohexyl-1-isopropoxyethoxycarbonyl, 1-cyclohexyl-1-cyclohexyloxy B Oxycarbonyl, 1-cyclohexyl-1-phenoxyethoxycarbonyl, 1-cyclohexyl-1-benzyloxyethoxycarbonyl, 1-phenyl-1-methoxyethoxycarbonyl, 1-phenyl-1-ethoxyethoxycarbonyl, 1-phenyl-1-n-propoxyethoxycarbonyl, 1-phenyl-1-isopropoxyethoxycarbonyl, 1-benzene -1-cyclohexyloxyethoxycarbonyl, 1-phenyl-1-phenoxyethoxycarbonyl, 1-phenyl-1-benzyloxyethoxycarbonyl, 1-benzyl-1 -methoxyethoxycarbonyl, 1-benzyl-1-ethoxyethoxycarbonyl, 1-benzyl-1-n-propoxyethoxycarbonyl, 1-benzyl-1-isopropoxy Ethyloxycarbonyl, 1-benzyl-1-cyclohexyloxyethoxycarbonyl, 1-benzyl-1-phenoxy Ethoxycarbonyl, 1-benzyl-1-benzyloxyethoxycarbonyl, etc.; as the group represented by the above formula (B-4), for example, 2-(2-methyltetrahydrofuranyl) An oxycarbonyl group, a 2-(2-methyltetrahydropyranyl)oxycarbonyl group or the like; and a group represented by the above formula (B-5): for example, a 1-methoxycyclopentyloxy group A carbonyl group, a 1-methoxycyclohexyloxycarbonyl group or the like.

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

The group represented by the following formula (B-6) is exemplified as the group of the 1-alkylcycloalkyl ester structure of the carboxylic acid.

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

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

The group represented by the above formula (B-6) includes, for example, 1-methylcyclopropoxycarbonyl group, 1-methylcyclobutoxycarbonyl group, 1-methylcyclopentyloxycarbonyl group, and 1- Methylcyclohexyloxycarbonyl, 1-methylcycloheptyloxycarbonyl, 1-methylcyclooctyloxycarbonyl, 1-methylcyclononyloxycarbonyl, 1-methylcyclononyloxycarbonyl, 1- Ethylcyclopropoxycarbonyl, 1-ethylcyclobutoxycarbonyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclohexyloxycarbonyl, 1-ethylcycloheptyloxycarbonyl, 1- Ethylcyclooctyloxycarbonyl, 1-ethylcyclodecyloxycarbonyl, 1-ethylcyclodecyloxycarbonyl, 1-(iso)propylcyclopropoxycarbonyl, 1-(iso)propylcyclobutane Oxycarbonyl, 1-(iso)propylcyclopentyloxycarbonyl, 1-(iso)propylcyclohexyloxycarbonyl, 1-(iso)propylcycloheptyloxycarbonyl, 1-(iso)propyl Cyclooctyloxycarbonyl, 1-(iso)propylcyclodecyloxycarbonyl, 1-(iso)propylcyclodecyloxycarbonyl, 1-(iso)butylcyclopropoxycarbonyl, 1-(iso) Butylcyclobutoxycarbonyl, 1-(iso)butylcyclopentyloxycarbonyl, 1-(iso)butylcyclohexyloxycarbonyl, 1-(iso)butylcycloheptyloxycarbonyl, 1-( Isobutyl octyloxycarbonyl, 1 -(iso)butylcyclomethoxycarbonyl, 1-(iso)butylcyclomethoxycarbonyl, 1-(iso)pentylcyclopropoxycarbonyl, 1-(iso)pentylcyclobutoxycarbonyl , 1-(iso)pentylcyclopentyloxycarbonyl, 1-(iso)pentylcyclohexyloxycarbonyl, 1-(iso)pentylcycloheptyloxycarbonyl, 1-(iso)pentylcyclooctyloxy Carbocarbonyl, 1-(iso)pentylcyclodecyloxycarbonyl, 1-(iso)pentylcyclodecyloxycarbonyl, 1-(iso)hexylcyclopropoxycarbonyl, 1-(iso)hexylcyclobutoxy Carbocarbonyl, 1-(iso)hexylcyclopentyloxycarbonyl, 1-(iso)hexylcyclohexyloxycarbonyl, 1-(iso)hexylcycloheptyloxycarbonyl, 1-(iso)hexylcyclooctyloxycarbonyl , 1-(iso)hexylcyclodecyloxycarbonyl, 1-(iso)hexylcyclodecyloxycarbonyl, 1-(iso)heptylcyclopropoxycarbonyl, 1-(iso)heptylcyclobutoxycarbonyl , 1-(iso)heptylcyclopentyloxycarbonyl, 1-(iso)heptylcyclohexyloxycarbonyl, 1-(iso)heptylcycloheptyloxycarbonyl, 1-(iso)heptylcyclooctyloxy Carbocarbonyl, 1-(iso)heptylcyclodecyloxycarbonyl, 1-(iso)heptylcyclodecyloxycarbonyl, 1-(iso)octylcyclopropoxycarbonyl, 1-(iso)octyl ring Butoxycarbonyl, 1-(iso)octylcyclopentyloxycarbonyl, 1-(iso)octyl Hexyloxycarbonyl, 1-(iso)octylcycloheptyloxycarbonyl, 1-(iso)octylcyclooctyloxycarbonyl, 1-(iso)octylcyclodecyloxycarbonyl, 1-(iso)octyl A base ring methoxycarbonyl group or the like.

The tributyl acrylate-containing group of the above carboxylic acid means a tertiary butyloxycarbonyl group.

The compound of the [B] ester-containing structure in the present invention is preferably a compound represented by the following formula (B).

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 tertiary butyloxycarbonyl group, n is 2 and R is a single bond, or n is 2 An integer of ～10 and R is an n-valent group obtained by removing hydrogen from a heterocyclic compound having 3 to 10 carbon atoms or an n-valent hydrocarbon group having 1 to 18 carbon atoms.

As n, it is preferably 2 or 3.

Specific examples of R in the above formula (B) include, when n is 2, a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, and 1,2-benzene extending benzene. Base, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 5-sodium sulfo-1,3-phenylene, 5-tetrabutylphosphonium sulfonate-1 Further, when n is 3, a group represented by the following formula, a benzene-1,3,5-triyl group or the like can be given.

As the above alkylene group, it is preferably linear.

The [B] ester-containing structure compound represented by the above formula (B) can be synthesized by a conventional method of organic chemistry or a conventional method in which organic chemistry is appropriately combined.

For example, the group B in the above formula (B) is a compound of the group represented by the above formula (B-1) (in the case where R ₁₃ is removed as a phenyl group), preferably in the presence of a phosphoric acid catalyst, By the compound R-(COOH) _n (wherein R and the respectively defined as in the above formula (B)) and the compound R ₁₄ -O-CH=R ₁₃ ' (wherein R ₁₄ and the above formula (B-) The definition in 1) is the same, and R _{13 '} is a group obtained by removing a hydrogen atom from a single carbon of the group R ₁₃ in the above formula (B-1).

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

In the formula, n1 is the same as defined in the above formula (B-2).

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

<[C] component: at least one selected from the group consisting of polyproline and polyimine >

The organic semiconductor alignment composition preferably contains at least one polymer selected from the group consisting of polyproline and polyimine. By including the polymer, the composition can improve the insulating properties of the obtained alignment film for an organic semiconductor. Further, while providing thermal stability and chemical stability, the adhesion to the insulating layer is also good.

Hereinafter, at least one polymer selected from the group consisting of polyproline and polyimine will be described in the order of polyproline and polyimine.

(polyglycine)

The above polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.

Examples of the tetracarboxylic dianhydride which can be used for the synthesis of polyamic acid include, for example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic 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-tricarboxyl Alkane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo 3--3-furyl)-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, 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) to (F-14), respectively, an aliphatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride;

Benzene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl fluorene tetracarboxylic 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'-dimethyldiphenyldecane tetracarboxylic dianhydride , 3,3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxybenzene Oxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy Diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, two (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylphthalic acid) dianhydride, two (triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, the following formula (F- 15) to (F-18), an aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride or the like.

Preferred among these are 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-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,3 - dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, benzene tetracarboxylic dianhydride, 3,3 ',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3' 4,4'-biphenyl ether tetracarboxylic dianhydride or tetracarboxylic dianhydride represented by the above formulas (F-1), (F-2) and (F-15) to (F-18), respectively. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

As the diamine compound which can be used for the synthesis of poly-proline, for example, p-phenylenediamine, meta-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-diaminobenzoquinone, 4,4'-diaminodiphenyl ether, 4,4'-diamino-2,2'-dimethyl linkage Benzene, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3 ,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3,4'-diaminodiphenyl ether , 2,2-bis(4-aminophenoxy)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-di[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]碸, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-Asia Methyl-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamine 5-,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylene isopropylidene) Bis(aniline), 4,4'-(m-phenylphenylidene)bis(aniline), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)benzene Hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl) Phenoxy]-octafluorobiphenyl, 6-(4-chalconeoxy)hexyloxy (2,4-diaminobenzene), 6-(4'-fluoro-4-chalcone Oxy)hexyloxy (2,4-diaminobenzene), 8-(4-chalconeoxy)octyloxy (2,4-diaminobenzene), 8-(4'-fluoro 4-chalconenyloxy)octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy -2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-18 Alkyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, twelve Alkyloxy (3,5-diaminobenzoic acid) Mercapto), tetradecyloxy (3,5-diaminobenzimidyl), pentadecyloxy (3,5-diaminobenzimidyl), hexadecyloxy ( 3,5-diaminobenzimidyl), octadecyloxy (3,5-diaminobenzimidyl), cholesteryloxy (3,5-diaminobenzimidyl) , cholesteryloxy (3,5-diaminobenzimidyl), (2,4-diaminophenoxy) palmitate, (2,4-diaminophenoxy) a stearic acid ester, a (2,4-diaminophenoxy)-4-trifluoromethylbenzoate, and a diamine compound represented by the following formula (G-1) to (G-5) Group diamine

An aromatic diamine having a hetero atom such as diaminotetraphenylthiophene; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and seven Methylenediamine, octamethyldiamine, 9-methylenediamine, 4,4-diaminoheptamethyldiamine, 1,4-diaminocyclohexane, cyclohexane bis(methylamine) , tetrahydrodicyclopentadiene diamine, isophorone diamine, hexahydro-4,7-bridged methylene fluorenylene (methano indenylidene) dimethylene diamine, subtricyclic [6.2. 1.0 ^2,7 ] an undecyl dimethyl diamine, an aliphatic diamine such as 4,4′-methylene bis(cyclohexylamine) or an alicyclic diamine; diamino hexamethyldioxane Iso-diamine-based organooxane and the like.

Preferred among these are p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4,4'-diamino-2,2'-dimethylbiphenyl. , cyclohexane bis(methylamine), 1,5-diaminonaphthalene, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 4,4'- Phenyl isopropylidene)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane 2,2-bis[4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-di(trifluoro Methyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 1-hexadecyloxy-2,4-di Aminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4- Diaminobenzene, hexadecyloxy (3,5-diaminobenzimidamide), octadecyloxy (3,5-diaminobenzimidamide), cholesteryloxy group (3,5 -diaminobenzimidamide), cholesteryloxy group (3,5-diaminobenzimidazole) or a diamine represented by the above formula (G-1) to (G-5). These diamines may be used alone or in combination of two or more.

The ratio of use of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of polylysine is preferably 0.2 to the acid anhydride group of the tetracarboxylic dianhydride per 1 equivalent of the amine group contained in the diamine compound. The ratio of 2 equivalents is more preferably 0.3 to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 to 150 ° C, more preferably at a temperature of 0 to 100 ° C, preferably 0.5 to 24 hours, more preferably Carry out 2 to 10 hours. In addition, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyaminic acid, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N. Aprotic, such as N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine A polar solvent; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount of the organic solvent (a) is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine (b) is 0.1 to 50% by mass, more preferably 5 to 30% by mass based on the total amount of the reaction solution (a+b). The amount of %.

As described above, a reaction solution in which polylysine is dissolved can be obtained. The reaction solution may be directly used for preparing an organic semiconductor alignment composition, or may be used to prepare an organic semiconductor alignment composition after separating the polyamic acid contained in the reaction solution, or after separating the separated polyamic acid. For the preparation of an organic semiconductor alignment composition. The separation of the polyamic acid can be carried out by injecting the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or by subjecting the solvent in the reaction solution to distillation under reduced pressure. Alternatively, the polypeptone may be purified by re-dissolving the polylysine in an organic solvent and then precipitating it in a poor solvent; or by repeating the step of distilling off one or more times with an evaporator under reduced pressure. Amino acid.

(polyimine)

The above polyimine can be produced by dehydrating and ring-closing the structure of the proline which the polyamic acid obtained above has. At this time, the proline structure can be completely dehydrated and closed, and the ruthenium can be completely imidized; or a part of the structure of the proline can be dehydrated and closed to form a part of the guanidine structure and the quinone ring structure. Amine.

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

The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. By setting the reaction temperature to 50 ° C or higher, the dehydration ring closure reaction can be sufficiently carried out, and by lowering the reaction temperature to 200 ° C or lower, the molecular weight of the obtained ruthenium iodide polymer can be suppressed. The reaction time in the method of heating the polyamic acid is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours.

On the other hand, in the method of adding the dehydrating agent and the dehydration ring-closure catalyst to the polyaminic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the polyamic acid structural unit. Further, examples of the dehydration ring-closure catalyst include tertiary amines such as pyridine, trimethylpyridine, lutidine, and triethylamine. However, it is not limited to this. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours.

In the above method (ii), as described above, a reaction solution containing polyimine can be obtained. The reaction solution may be directly used for preparing an organic semiconductor alignment composition, or may be used for preparing an organic semiconductor alignment composition after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and after separating the polyimine. For preparing an organic semiconductor alignment composition; or after purifying the separated polyimine, it is used for preparing an organic semiconductor alignment composition. In order to remove the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement is suitably employed. The separation and purification of the polyimine can be carried out by the same operation as described above for the separation and purification of the polyamic acid.

In the organic semiconductor alignment composition of the present invention, in addition to the photo-alignment polyorganosiloxane compound, at least one polymer selected from the group consisting of poly-proline and polyimine. The total suitable ratio of the polyamic acid and the polyimine is from 100 to 5,000 parts by mass, more preferably from 200 to 2,000 parts by mass, per 100 parts by mass of the photo-aligned polyorganosiloxane compound.

(other polymers)

The above other polymers can be used to further improve the solution properties of the organic semiconductor alignment composition of the present invention and the electrical properties of the resulting organic semiconductor alignment film. Examples of the other polymer include a polyorganosiloxane having a repeating unit having a different structure from the repeating unit represented by the above formula (3), and a condensate of a hydrolyzate and a hydrolyzate thereof. At least one selected (hereinafter, referred to as "other polyorganosiloxane"), polyphthalate, polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(benzene) Ethylene-phenylmaleimide derivatives, poly(meth)acrylates, and the like.

(other polyorganosiloxane)

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

In the 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 It is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

Further, when the organic semiconductor alignment composition contains other polyorganosiloxanes, most of the other polyorganosiloxanes are independently present and the photo-aligned polyorganosiloxane compound is independently present, and the other portion is photo-aligned polyorganoindene. The form of the condensate of the oxyalkyl compound is present.

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

As the raw material decane compound which can be used herein, for example, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, and tetra-di are mentioned. Grade butoxy oxane, tetra-tertiary butoxy decane, tetrachloro decane; methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl triisopropoxy Decane, methyl tri-n-butoxydecane, methyl tri- or 2-butoxybutane, methyl tertiary butoxydecane, methyltriphenyloxydecane, methyltrichlorodecane, ethyltrimethoxy Decane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltriisopropoxydecane, ethyltri-n-butoxydecane, ethyltri-butoxybutane, ethyl Tri-tertiary butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro decane; dimethyl dimethoxy decane, dimethyl di Oxydecane, dimethyl dichlorodecane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chlorodecane, and the like. Among them, preferred are tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, and Methyl dimethoxy decane, dimethyl diethoxy decane, trimethyl methoxy decane or trimethyl ethoxy decane.

In the case of synthesizing another polyorganosiloxane, the organic solvent which can be used arbitrarily may, for example, be an alcohol compound, a ketone compound, a guanamine compound or an ester compound or other aprotic compound. They may be used alone or in combination of two or more.

Examples of the above alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isoamyl alcohol, and 2-methyl. Butanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol, secondary heptanol, g 3-ol, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-nonanol, second undecyl alcohol, three Methyl decyl alcohol, secondary tetradecyl alcohol, secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol Monohydric alcohol compound; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexane Polyol compound such as alcohol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, B Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl , 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 A partial ether of a polyol compound such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monopropyl ether. These alcohol compounds may be used singly or in combination of two or more kinds thereof as the above ketone compound, and examples thereof include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, and diethyl ketone, respectively. Methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, diisobutyl ketone, methyl n-hexyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methyl Monoketone compounds such as cyclohexanone, 2,4-pentanedione, fenchone, acetophenone, acetone acetone; etidylacetone, 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- Beta-dione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione Ketone compounds and the like. These ketone compounds may be used alone or in combination of two or more.

Examples of the above guanamine compound include formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, and N,N-diethylformamidine. Amine, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropionamidine Amine, N-methylpyrrolidone, N-methyl fluorenyl Porphyrin, N-methylpyridyl piperidine, N-methylpyridyl pyrrolidine, N-ethyl fluorenyl Porphyrin, N-ethinylpiperidine, N-ethinylpyrrolidine, and the like. These guanamine 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, and acetic acid. Propyl ester, n-butyl acetate, isobutyl acetate, n-butyl acetate, n-amyl acetate, diethyl amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, acetic acid 2- Ethyl butyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl ethyl acetate, ethyl acetate, ethyl acetate Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, Ethylene glycol diacetate, methoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, Diethyl dicarboxylate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, dimethyl phthalate, phthalic acid Ethyl ester and the like. These ester compounds may be used alone or in combination of two or more.

Examples of the other aprotic compound include acetonitrile, dimethyl hydrazine, N, N, N', N'-tetraethyl thio amide, trimethylamine hexamethyl phosphate, and N-methyl group. Linoleone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrrolidine, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylper , 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.

Among these solvents, a polyol compound or a partial ether or ester compound of a polyol compound is particularly preferred.

The amount of water used in the synthesis of the other polyorganosiloxane is preferably from 0.01 to 100 mol, more preferably from 0.1 to 30 mol, further more than 1 mol of the total of the alkoxy group and the halogen atom which the starting decane compound has. Good is 1~1.5mol ratio.

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

The metal chelate compound may, for example, be triethoxy ‧ mono(ethyl decyl pyruvate) titanium, tri-n-propoxy group, mono (ethyl acetonate pyruvate) titanium, triisopropoxy ‧ Mono(acetylthiopyruvate) titanium, tri-n-butoxy ‧ mono(ethyl decyl pyruvate) titanium, tri- or two-dimensional butoxy ‧ mono (ethyl phthalate) titanium, three - three Grade butoxy. mono (acetylthiopyruvate) titanium, diethoxy bis (ethyl phthalate) titanium, di-n-propoxy bis (ethyl phthalate) titanium, two Isopropoxy bis(ethyl decyl pyruvate) titanium, di-n-butoxy bis(ethyl decyl pyruvate) titanium, di- or two-butoxy bis (ethyl decyl pyruvate) Titanium, di-tertiary butoxy bis(acetylthiopyruvate) titanium, monoethoxy ‧ tris(acetylsulfonate) titanium, mono-n-propyloxy ‧ tris(acetylpyruvate) Salt) titanium, mono-isopropoxy ‧ tris(acetylthiopyruvate) titanium, mono-n-butoxy ‧ tris(acetylpyruvate) titanium, mono- s-butoxy ‧ three (B) Mercapto pyruvate) titanium, mono-tertiary butoxy ‧ tris(acetylthiopyruvate) titanium, tetrakis(ethylpyruvate) titanium, three Oxy ‧ mono (acetic acid ethyl acetate) titanium, tri-n-propoxy ‧ single (acetic acid ethyl acetate) titanium, triisopropoxy ‧ single (acetic acid ethyl acetate) titanium, tri-n-butoxy ‧Single (acetic acid ethyl acetate) titanium, tri- or 2-butoxybutane mono(acetonitrile ethyl acetate) titanium, tris-tertiary butoxy ‧ single (acetic acid ethyl acetate) titanium, diethoxy Base ‧ (acetate ethyl acetate) titanium, di-n-propoxy bis (acetic acid ethyl acetate) titanium, diisopropoxy ‧ bis (acetic acid ethyl acetate) titanium, di-n-butoxy ‧ Di(acetonitrile ethyl acetate) titanium, di- or 2-butoxy-bis(acetic acid ethyl acetate) titanium, di-tertiary butoxy bis(acetic acid ethyl acetate) titanium, monoethoxy ‧ tris(acetate ethyl acetate) titanium, mono-n-propoxy ethoxylate (acetic acid ethyl acetate) titanium, monoisopropoxy ‧ tris(ethyl acetate) titanium, mono-n-butoxy ‧ three (Ethyl acetate, ethyl acetate) Titanium, mono-?-butoxy-tris-(triethylacetate) titanium, mono-tertiary butoxy-tris(ethyl acetate) titanium, tetrakis(acetonitrile) Ethyl ester) titanium, mono(ethyl decyl pyruvate) tris(acetate ethyl acetate) titanium, bis(ethyl phthalate pyruvate) di(acetate ethyl acetate) titanium, three (B)醯-pyruvate) mono(acetonitrile ethyl acetate) titanium chelate such as titanium; triethoxy ‧ mono (ethyl decyl pyruvate) zirconium, tri-n-propoxy ‧ single (acetyl thiopyruvate Salt) zirconium, triisopropoxy ‧ mono (ethyl decyl pyruvate) zirconium, tri-n-butoxy ‧ mono (ethyl decyl pyruvate) zirconium, tri- or two-butoxy ‧ single (acetyl Pyruvate, zirconium, tris-tertiary butoxy, mono(ethylpyruvate) zirconium, diethoxy bis(ethyl decyl pyruvate) zirconium, di-n-propoxy ‧ Ethyl pyruvate) zirconium, diisopropoxy ‧ bis (ethyl decyl pyruvate) zirconium, di-n-butoxy bis (ethyl decyl pyruvate) zirconium, di- or 2-butoxy ‧ bis(ethyl decyl pyruvate) zirconium, zirconium di-tert-butoxy bis(ethyl decyl pyruvate), zirconium monoethoxy ‧ tris(ethyl decyl pyruvate), single positive Oxygen ‧ tris(acetylthiopyruvate) zirconium, monoisopropoxy ‧ tris(ethyl decyl pyruvate) zirconium, mono-n-butoxy ‧ tris(ethyl decyl pyruvate) zirconium, single two Grade butoxy ‧ tris(ethyl decyl pyruvate) zirconium, mono-tertiary butoxy ‧ tris(ethyl decyl pyruvate) ruthenium, tetrakis (acetyl acetonate) Zirconium, triethoxy ‧ mono (acetic acid ethyl acetate) zirconium, tri-n-propoxy ‧ mono (acetic acid ethyl acetate) zirconium, triisopropoxy ‧ single (acetic acid ethyl acetate) zirconium, three n-Butyloxy ‧ mono(acetic acid ethyl acetate) zirconium, tri- or 2-butoxybutane mono(acetonitrile ethyl acetate) zirconium, tri-tertiary butoxy ethoxy (ethyl acetate) zirconium , diethoxy bis (acetic acid ethyl acetate) zirconium, di-n-propoxy bis (acetic acid ethyl acetate) zirconium, diisopropoxy ‧ bis (acetic acid ethyl acetate) zirconium, two positive Zirconium tert-butyl (acetate ethyl acetate) zirconium, zirconium di- or di-butoxy bis(acetonitrile), zirconium di-tertiary butoxy bis(acetonitrile), zirconium, Zirconium monoethoxy ethoxylate (ethyl acetate), zirconium mono-n-propoxy ethoxylate (ethyl acetate), zirconium monoisopropoxy ethoxylate (ethyl acetate), mono-n-butyl Oxygen ‧ tris(ethyl acetate) zirconium, mono-s-butoxy ‧ tris(ethyl acetate) zirconium, mono-tertiary butoxy ‧ tris(ethyl acetate) zirconium, tetra (b)醯 ethyl acetate) zirconium, mono(ethyl decyl pyruvate) tris(ethyl acetate) zirconium, bis(ethyl decyl pyruvate) bis (acetic acid ethyl acetate) , tris(acetylsulfonate) monozide (acetic acid ethyl acetate) zirconium chelate such as zirconium; aluminum chelate compound such as aluminum tris(ethylpyruvate), aluminum tris(acetate) Wait.

Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, adipic acid, and methylmalonic acid. Azelaic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic 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, Fumar Acid, citric acid, tartaric acid, etc.

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

Examples of the above organic base include pyridine, pyrrole, and piperidine. , pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, Diazabicyclodecane, diazabicycloundecene, tetramethylammonium hydroxide, and the like.

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

Among these catalysts, a metal chelate compound, an organic acid or an inorganic acid is preferred. As the metal chelate compound, a titanium chelate compound is more 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, per 100 parts by mass of the starting decane compound.

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

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

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

(Use ratio of other polymers)

When the organic semiconductor alignment composition of the present invention contains the other polymer and the photo-aligned polyorganosiloxane compound, the content of the other polymer is compared with 100 parts by mass of the photo-aligned polyorganosiloxane compound. Preferably, it is 10,000 parts by mass or less. The more preferred content of other polymers will vary depending on the type of other polymer.

On the other hand, when the organic semiconductor alignment composition of the present invention contains a photo-alignment polyorganosiloxane compound and other polyorganosiloxane, the preferred ratio of use is relative to 100 parts by mass of optical alignment. The polyorganosiloxane compound, the amount of other polyorganosiloxane is 100 to 2,000 parts by mass. When the organic semiconductor alignment composition of the present invention contains a photo-alignment polyorganosiloxane compound and another polymer, the type of the other polymer is preferably another polyorganosiloxane.

(curing agent and curing catalyst, and curing accelerator)

In order to make the crosslinking reaction of the photo-alignment polyorganosiloxane compound stronger, the curing agent and the curing catalyst may be contained in the organic semiconductor alignment composition of the present invention. The curing accelerator may be contained in the organic semiconductor alignment composition of the present invention for the purpose of promoting the curing reaction of the curing agent.

As the curing agent, a curing agent which is usually used for curing of a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used. As such a curing agent, for example, a polyamine, a polycarboxylic acid anhydride, or a polyvalent carboxylic acid can be exemplified.

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

Specific examples of the cyclohexanetricarboxylic anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3, 5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc., and other polycarboxylic acid anhydrides, for example, 4-methyltetrahydrophthalic anhydride, methylnaphthalene Dicic anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, a compound represented by the following formula (6),

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

a tetracarboxylic dianhydride commonly used in the synthesis of polylysine, and an alicyclic compound having a conjugated double bond such as α-pinene or bellerol and a Diels-Alder reaction product of maleic anhydride and hydrogen thereof Additives, etc.

As the curing catalyst, for example, a ruthenium hexafluoride compound, a phosphorus hexafluoride compound, aluminum triethyl acetyl phthalate or the like can be used. These catalysts can be cationically polymerized by heating a catalytic epoxy group.

The curing accelerator may, for example, be an imidazole compound; a quaternary phosphonium compound; a quaternary amine compound; and a compound such as 1,8-diazobicyclo[5.4.0]undecene-7 and an organic acid salt thereof. Azobicycloalkenes; organometallic compounds such as zinc octoate, tin octoate, acetonitrile aluminum complex; boron compounds such as boron trifluoride or triphenyl borate; like zinc chloride, tin chloride Such a metal halide; a high-melting-point-dispersion latent curing accelerator such as an amine addition-forming accelerator such as dicyanodiamine, an amine and an epoxy resin; and a surface polymerization of a quaternary phosphonium salt or the like Microcapsule-type latent curing accelerator formed by covering; amine salt type latent curing accelerator; pyrolysis type thermal cationic polymerization type late curing like Lewis acid salt, Bronsted acid salt Promoters, etc.

(epoxy compound)

The epoxy compound can be contained in the organic semiconductor alignment composition of the present invention from the viewpoint of further improving the adhesion of the formed organic semiconductor alignment film to the surface of the insulating film.

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

When the organic semiconductor alignment composition of the present invention contains an epoxy compound, the content thereof is preferably 0.01 to 40 parts by mass based on 100 parts by mass of the photo-aligned polyorganosiloxane compound and any other polymer used arbitrarily. The amount is preferably 0.1 to 30 parts by mass or less.

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

(functional decane compound)

The above functional decane compound can be used for the purpose of further improving the adhesion between the obtained organic semiconductor alignment film and the substrate or the gate. The functional decane compound may, for example, be a functional decane compound, and examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyltrimethyl. Oxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxydecane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethyl Oxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxymethylidenepropyltriethylenetriamine, N-trimethoxycarbamidopropyl Triethylene triamine, 10-trimethoxycarbamimidyl-1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9 -trimethoxycarbamido-3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3 -Aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N- 3-aminopropyltriethoxydecane, N-di(oxyethyl)-3-aminopropyltrimethoxydecane, N-di(oxidized ethyl)-3-aminopropyl Further, triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-glycidylpropyltrimethoxydecane, and the like, and Japanese Patent Laid-Open No. 63- A reaction product of a tetracarboxylic dianhydride and a decane compound having an amine group described in Japanese Patent Publication No. 291922.

When the functional composition of the organic semiconductor of the present invention contains a functional decane compound, the content thereof is 100 parts by mass, preferably 50, based on the photo-aligned polyorganosiloxane compound and any other polymer used arbitrarily. It is more preferably 20 parts by mass or less.

(surfactant)

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, an organic ruthenium surfactant, a polyalkylene oxide surfactant, and a fluorine-containing surfactant. Surfactant and the like.

When the organic semiconductor alignment composition contains a surfactant, the content thereof is preferably 10 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the total of the organic semiconductor alignment composition.

(photosensitizing compound)

The photosensitizing compound which can be contained in the organic semiconductor alignment composition has a carboxyl group, a hydroxyl group, -SH, -NCO, -NHR (wherein R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) And at least one selected from the group consisting of -CH=CH ₂ and SO ₂ Cl and a compound of a photo-sensitizing structure. By reacting the above-mentioned epoxy group-containing polyorganosiloxane with a mixture of a specific cinnamic acid derivative and a photo-sensitizing compound, the photo-aligned polyorganosiloxane compound contained in the composition for organic semiconductor alignment of the present invention A photosensitive structure (cinnamic acid structure) derived from a specific cinnamic acid derivative and a photo-sensitizing structure derived from a photo-sensitizing compound. The light-sensitizing structure has a function of providing a photosensitive structure close to the excitation energy in the polymer by excitation by light irradiation. The excited state may be singlet or tri-state, but is preferably tri-stated in view of long life and efficient energy movement. The light absorbed by the light-sensitizing structure is preferably ultraviolet light or visible light having a wavelength in the range of 150 to 600 nm. Light having a wavelength shorter than the above lower limit cannot be applied to the optical alignment method because it cannot be processed in a normal optical system. On the other hand, light having a wavelength longer than the above upper limit has a small energy, and it is difficult to excite the excited state of the above-described light-sensitizing structure.

Examples of the photo-sensitizing structure include an acetophenone structure, a benzophenone structure, a fluorene structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, an anthracene structure, a naphthalene structure, an anthracene structure, and an anthracene structure. A pyridine structure, an anthracene structure, or the like may be used alone or in combination of two or more. These photo-sensitizing structures are removed from acetophenone, benzophenone, anthracene, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, anthracene, anthracene, acridine or anthracene, respectively. A structure formed by a group of 1 to 4 hydrogen atoms. Wherein, the acetophenone structure, the carbazole structure and the fluorene structure are each preferably formed by a group obtained by removing 1 to 4 of the hydrogen atoms of the benzene ring of acetophenone, carbazole or anthracene. structure. Among these light-sensitizing structures, preferred are selected from the group consisting of an acetophenone structure, a benzophenone structure, a fluorene structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, and a naphthalene structure. At least one, particularly preferably at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, and a nitroaryl structure.

The photo-sensitizing compound is preferably a compound having a carboxyl group and a photosensitizing structure, and a compound represented by the following formulas (H-1) to (H-10), for example, may be mentioned as a more preferable compound.

In the formula, q is an integer from 1 to 6.

The photo-aligned polyorganosiloxane compound used in the present invention is obtained by combining the polyorganosiloxane having an epoxy group and a specific cinnamic acid derivative and a photo-sensitizing compound as described above, preferably in the presence of a catalyst. Next, it is preferred to carry out a reaction synthesis 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 1 to mol of the fluorene atom of the polyorganosiloxane having an epoxy group. It is used in the range of 0.2 to 0.9 mol. The photo-sensitizing compound is preferably 0.0001 to 0.5 mol, more preferably 0.0005 to 0.2 mol, still more preferably 0.001 to 0.1 mol, per mol of the fluorene atom of the polyorganosiloxane having an epoxy group. Range used.

(Preparation of composition for organic semiconductor alignment)

As described above, the organic semiconductor alignment composition of the present invention contains a photo-alignment polyorganosiloxane compound as an essential component, and may contain other optional components as needed. Preferably, each component is dissolved in an organic solvent to prepare a solution. Shaped composition. In addition, the photo-aligned polyorganosiloxane compound and other components (for example, at least one polymer selected from the group consisting of poly-proline and polyimine, and other polyorganosiloxanes) In any state of the organic semiconductor alignment composition and the organic semiconductor alignment film, a part of them may be connected to each other.

As the organic solvent which can be used for blending the organic semiconductor alignment composition of the present invention, a solvent which dissolves the photoalignment polyorganosiloxane compound and other components used without reacting with them is preferable. The organic solvent which can be preferably used in the organic semiconductor alignment composition of the present invention varies depending on the type of other polymer to be added.

In the organic semiconductor alignment composition of the present invention, the organic solvent exemplified as the solvent for synthesizing polyglycine is exemplified as the preferred organic solvent with respect to the photo-alignment polyorganosiloxane compound. . In this case, it can also be used together with the poor solvent exemplified as the organic solvent used for the synthesis of the polyamic acid of the present invention. These organic solvents may be used singly or in combination of two or more.

On the other hand, when the organic semiconductor alignment composition of the present invention contains a photoalignment polyorganosiloxane compound and another polyorganosiloxane as a polymer, preferred examples of the organic solvent include 1-B. Oxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, Dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl Ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl card Alcohol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate , n-amyl acetate, pentyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethyl butyl acetate Acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate and the like. Among them, preferred are n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate, n-pentyl acetate, and pentyl acetate.

A preferred solvent to be used in the preparation of the organic semiconductor alignment composition of the present invention can be obtained by combining one or two or more kinds of the above organic solvents depending on the presence or absence of other polymers and their types. In such a solvent, the components contained in the organic semiconductor alignment composition are not precipitated at a preferred solid concentration, and the surface tension of the organic semiconductor alignment composition is in the range of 25 to 40 mN/m.

The solid content concentration of the organic semiconductor alignment composition of the present invention, that is, the ratio of the mass of all components other than the solvent in the organic semiconductor alignment composition to the total mass of the organic semiconductor alignment composition, and the viscosity and volatility are considered. When it is selected, it is preferably in the range of 1 to 10% by mass. The organic semiconductor alignment composition of the present invention is applied onto an insulating film or applied to a substrate to cover the gate to form a coating film formed of an organic semiconductor alignment film, but when the solid content concentration is 1% by mass or more The film thickness of the coating film is not easily too 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, the film thickness of the coating film can be suppressed from being excessively large, and a favorable organic semiconductor alignment film can be obtained, and the viscosity of the organic semiconductor alignment composition can be prevented from increasing. The application is good. The range of the solid content concentration which is particularly preferable varies depending on the method used when the composition for organic semiconductor alignment is applied to the insulating film or the substrate. For example, when it is carried out by a spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When the printing method is used, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, whereby the solution viscosity is in the range of 12 to 50 mPa·s. When the inkjet method is used, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by mass, whereby the solution viscosity is in the range of 3 to 15 mPa·s.

The temperature at which the organic semiconductor alignment composition of the present invention is prepared is preferably from 0 ° C to 200 ° C, more preferably from 0 ° C to 40 ° C.

(Organic semiconductor alignment film)

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

As a method of forming the organic semiconductor alignment film, for example, an insulating film is formed on a substrate on which a gate is formed, a coating film of the organic semiconductor alignment composition of the present invention is formed on the insulating film, or a substrate on which a gate is formed. The coating film of the organic semiconductor alignment composition of the present invention is formed thereon, and then the coating film is irradiated with an optical alignment method having anisotropic polarization or the like to impart an alignment energy to the organic semiconductor molecule.

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

Next, the coating film is irradiated with linearly polarized or partially polarized light or unpolarized light to impart an alignment energy to the organic semiconductor molecule. 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, and ultraviolet light containing light having a wavelength of 300 nm to 400 nm is preferable. When the used light is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction, or may be performed in combination. When illuminating unpolarized light, the direction of illumination must be oblique.

As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light having a wavelength region as described above can be obtained by a mechanism for using the light source together with, for example, a filter, a diffraction grating, or the like.

Light irradiation amount is not particularly limited, but is preferably 1J / m ² or more and less 10,000J / m ^2, more preferably 10 ~ 3,000J / m ^2. In addition, when the organic semiconductor molecule is provided with an alignment energy on a coating film formed of a composition known for organic semiconductor alignment by a photo-alignment method, a light irradiation amount of 10,000 J/m ² or more is required. However, when the organic semiconductor alignment composition of the present invention is used, the radiation irradiation amount in the photo-alignment method is preferably 3,000 J/m ² or less, and further 1,000 J/m ² or less, and good organic semiconductor molecular alignment energy can be imparted. It contributes to improving the productivity of organic semiconductor components and reducing manufacturing costs.

The organic semiconductor alignment film thus formed causes the photoalignment polyorganosiloxane compound to have a low polarity, or the photo-alignment group is biased to the vicinity of the surface of the organic semiconductor alignment film. In particular, in the organic semiconductor alignment film, the group having a cinnamic acid structure is preferably in a range from the surface to a film thickness of 30%. The group having a cinnamic acid structure which contributes to the alignment of the organic semiconductor can more effectively induce the alignment of the organic semiconductor molecules by being biased in the vicinity of the surface of the organic semiconductor side of the alignment film.

When the composition for organic semiconductor alignment is applied, in order to improve the adhesion between the insulating film and the coating film, a functional decane compound, titanate or the like may be applied to the insulating film in advance.

(organic semiconductor component)

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

While a voltage (source-drain voltage) is applied between the source 6 and the drain 7 of the organic semiconductor element, if the voltage applied to the gate 3 (gate voltage: Vg) is changed, the organic semiconductor layer 8 and The amount of charge (carrier) in the interface of the alignment film 5 depends on the gate voltage variation, and the current (source-drain) flowing through the portion (channel) of the organic semiconductor layer 8 between the source 6 and the drain 7 can be changed. Current)). Thus, in the organic semiconductor element, the gate current Id can be controlled by controlling the gate voltage Vg.

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

When a voltage (source-drain voltage) is applied between the source 13 and the drain 14 of the organic semiconductor element, if the voltage applied to the gate 11 (gate voltage: Vg) is changed, the organic semiconductor layer 15 and the gate In the interface of the pole insulating film 12, the amount of charge (carrier) depends on the gate voltage change, and the current flowing through the portion (channel) of the organic semiconductor layer 15 between the source 13 and the drain 14 (source-drain) Current). Thus, in the organic semiconductor element, the gate current Id can be controlled by controlling the gate voltage Vg.

The π-orbital conjugate plane or π-stack of the organic semiconductor material is closely related to the direction of movement of the carrier. In order to increase the mobility μ of the carrier in the organic semiconductor layer, not only the direction of the organic semiconductor molecules is uniform in one direction, but also the π-orbital conjugate plane or π-stacking is specified. In the organic semiconductor device of the present invention, the alignment film is aligned by the photo-alignment method, whereby anisotropy can be imparted to the alignment of the organic semiconductor molecules. Therefore, the π-orbital conjugate plane or π can be specified by microscopic arrangement of the organic semiconductor molecules. It is also possible to form an organic semiconductor alignment film having excellent flatness without uneven alignment, and it is possible to eliminate the frictional damage caused by friction, eliminate the problem of contamination and adhesion, and suppress the off-state current.

The insulating substrate is not particularly limited, and for example, an inorganic material such as glass or quartz, or an acrylic, an ethylene, an ester, a quinone, a urethane, a diazo, a cinnamyl, or the like can be used. An organic polymer such as a photosensitive polymer compound, polyvinylidene fluoride, polyethylene terephthalate or polyethylene, or an organic-inorganic hybrid material. Further, it is also possible to use two or more layers of these materials in combination, and it is effective for the purpose of improving the insulation pressure resistance.

The gate insulating film formed of the organic semiconductor device of the present invention may be one layer or two or more layers. As the material of the gate insulating film 4 formed of the organic semiconductor element 1 of Fig. 1, various known materials can be used in combination. The material to be known is not particularly limited, and inorganic materials such as SiO ₂ , SiN, Al ₂ O ₃ , and Ta ₂ O ₅ may be used, polyphthalic acid, polyimide, polyacrylonitrile, polytetrafluoroethylene, and poly. Organic materials such as vinyl alcohol, polyvinyl phenol, polyethylene terephthalate, polyvinylidene fluoride, and organic-inorganic hybrid materials. It is preferred to use an organic material from the viewpoint of being able to utilize a low-cost liquid phase process. Further, as the polyamic acid and the polyimine, the above polylysine and polyimine which can be contained in the organic semiconductor alignment composition can be used. In addition, the gate insulating film 12 formed of the organic semiconductor element 9 of FIG. 2 may be one or two or more layers, and at least one layer is an organic semiconductor alignment film formed of the organic semiconductor alignment composition containing the [C] component. As a material of the gate insulating film forming the other layers, a material similar to the material of the gate insulating film 4 formed as the organic semiconductor element 1 of FIG. 1 and the above-exemplified materials can be used.

The organic semiconductor molecule constituting the organic semiconductor layer of the organic semiconductor device of the present invention is not particularly limited as long as it is a conjugated compound having a conjugated double bond. For example, suitable are the compounds shown below: polyacetylene derivatives, polythiophene derivatives having a thiophene ring, poly(3-alkylthiophene) derivatives, poly(3,4-ethylenedioxythiophene) derivatives , polythiophene acetylene derivative, polyphenylene derivative having a benzene ring, polyparaphenylene acetylene derivative, polypyridine derivative having a nitrogen atom, polypyrrole derivative, polyaniline derivative, polyquinoline derivative a conjugated polymer compound; an oligomer represented by dimethylhexathiophene or tetrathiophene; an acene represented by anthracene, naphtacene, and pentacene; and a heap represented by a copper phthalocyanine derivative Organic molecule; discotic liquid crystal represented by triphenylene derivative; discotic liquid crystal represented by phenylnaphthalene derivative, benzothiazole derivative; and poly(9,9-dialkylfluorene-linked A thiophene) copolymer is a liquid crystal polymer or the like. Among them, the organic semiconductor molecule is not limited to this.

Among these organic semiconductor molecules, a polymer compound having the above conjugated structure is suitable from the viewpoint of a liquid phase process or the like. The molecular weight of the conjugated polymer compound is not particularly limited, and 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 a suitable dopant to adjust its electrical conductivity. Examples of the type of the dopant include electron-accepting I ₂ , Br ₂ , Cl ₂ , ICl, BF ₃ , PF ₅ , H ₂ SO ₄ , FeCl ₃ , and TCNQ (tetracyanoquinodimethane). Electronically, Li, K, Na, Eu, an alkyl sulfonate as a surfactant, an alkylbenzene sulfonate, and the like.

The gate, the source, and the drain used in the organic semiconductor device of the present invention are not particularly limited as long as they are conductors. As a constituent material of each electrode, for example, a metal material such as Al, Cu, Ti, Au, Pt, Ag, or Cr, or an inorganic material such as polycrystalline germanium, telluride, ITO (Indium Tin Oxide) or SnO ₂ may be used, which is heavily doped. A conductive polymer material represented by polypyridine, polyacetylene, polyaniline, polypyrrole, or polythiophene, and a conductive ink such as carbon particles or silver particles. In particular, when it is used for a flexible electronic paper or the like, each electrode is a conductive ink in which a conductive polymer, carbon particles, silver particles, or the like is dispersed, and the thermal expansion property is easily matched with the substrate.

(Method of Manufacturing Organic Semiconductor Element)

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

A method of producing an organic semiconductor device according to another embodiment of the present invention includes a coating film forming step of forming a coating film on the organic semiconductor alignment composition to cover a gate electrode formed on the substrate, and forming a source on the coating film And an electrode forming step of the drain electrode, and an organic semiconductor layer forming step of forming an organic semiconductor layer at least between the electrode and the drain, further comprising irradiating the coating film with a linear deflecting light to form an organic layer before the step of forming the organic semiconductor layer The step of a semiconductor alignment film.

The method of forming the gate insulating film and the organic semiconductor layer constituting the organic semiconductor device of the present invention is not particularly limited, and can be, for example, an electrolytic polymerization method, a casting method, a spin coating method, a screen printing method, a dip coating method, or a micro mold method. Formed by a micro mould method, a microcontact method, an inkjet method, a roll coating method, an LB method, or the like. Further, the method of forming each electrode may be a vacuum deposition method, a CVD method, an electron beam evaporation method, a resistance heating vapor deposition method, a sputtering method, or the like, depending on the material to be used.

In addition, they can form a pattern of a desired shape by photolithography and etching. In addition, soft etching and inkjet methods are also effective methods of patterning. Further, an electrode drawn from each electrode, a protective film, or the like can be formed as needed.

Example

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by the examples.

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

Column: Tosoh Corporation, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

Further, the raw material compound and the polymer are synthesized by repeating the synthesis route shown in the following synthesis example as needed, thereby ensuring the necessary amounts of the raw material compound and the polymer used in the following examples.

<Synthesis of polyorganosiloxane having an epoxy group>

[Synthesis Example 1]

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

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

¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, and an epoxy group-based peak having a theoretical strength was obtained in the vicinity of a chemical shift (δ) = 3.2 ppm, and it was confirmed that the epoxy group did not generate a pair in the reaction. reaction. The viscosity, Mw and epoxy equivalent of the obtained polyorganosiloxane having an epoxy group are shown in Table 1.

[Synthesis Example 2~3]

In the same manner as in Synthesis Example 1, except that the raw materials to be added were as shown in Table 1, a polyorganosiloxane having an epoxy group was obtained as a viscous transparent liquid. The Mw and epoxy equivalents of the obtained polyorganosiloxane having an epoxy group are shown in Table 1.

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

ECETS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

MTMS: methyltrimethoxydecane

PTMS: Phenyltrimethoxydecane

<Synthesis of specific cinnamic acid derivatives>

The synthesis reaction of the specific cinnamic acid derivative is carried out entirely in an inert atmosphere.

[Synthesis Example 4]

In a 500 mL three-necked flask equipped with a condenser, 20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris(2-methylphenyl)phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetone were added. amine. Next, 7 g of an acrylic mixed solution was added by a syringe and stirred. The mixed solution was further stirred with heating at 120 ° C for 3 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. After filtering the precipitate, the filtrate was poured into 300 mL of a 1 N aqueous hydrochloric acid solution, and the precipitate was collected. The precipitate was recrystallized from a 1:1 solution of ethyl acetate and hexane to give 8.4 g of the compound of the formula (K-1) (specific cinnamic acid derivative (K-1)).

[Synthesis Example 5]

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 tetrakis(triphenylphosphine)palladium, 4 g of sodium carbonate, 80 mL of tetrahydrofuran, and 39 mL of pure were mixed. water. Then, the reaction solution was heated and stirred at 80 ° C for 8 hours, and the completion of the reaction was confirmed by TLC. After the reaction solution was cooled to room temperature, 200 mL of a 1 N aqueous hydrochloric acid solution was poured, and the solid was separated by filtration. The obtained solid was dissolved in ethyl acetate, and washed with 100 mL of 1N aqueous hydrochloric acid, 100 mL of pure water, and 100 mL of saturated brine. Then, the organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated. 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 6]

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, and 11 g of triethylamine were mixed. 50 mL of dimethylacetamide. The solution was stirred with heating at 120 ° C for 3 hours, and after completion of the reaction by TLC, the reaction solution was cooled to room temperature. After filtering the precipitate, the filtrate was poured into 300 mL of a 1 N aqueous hydrochloric acid solution to recover a precipitate. The precipitate was recrystallized from ethyl acetate to give 4.1 g of the compound of the formula (K-3) (specific cinnamic acid derivative (K-3)).

[Synthesis Example 7]

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

[Synthesis Example 8]

91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone were placed in a 1 L eggplant type flask, and after stirring at room temperature for 1 hour, 99.7 g was added. 1-Bromopentane was stirred at 100 ° C for 5 hours. After the reaction was completed, it was precipitated again with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, it was neutralized with hydrochloric acid, and the resulting precipitate was recrystallized from ethanol to give white crystals of 102 g of 4-pentyloxybenzoic acid. 10.41 g of the obtained 4-pentyloxybenzoic acid was taken out into a reaction vessel, and 100 mL of sulfinium chloride and 77 mL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Next, sulfinium chloride was distilled off under reduced pressure, dichloromethane was added, and the mixture was washed with a sodium hydrogencarbonate aqueous solution, dried over magnesium sulfate Next, in a 500 mL three-necked flask different from the above, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran, and 100 mL of water were added. The aqueous solution was ice-cooled, and the above tetrahydrofuran solution was slowly added dropwise, followed by stirring for 2 hours to carry out a reaction. After completion of the reaction, the mixture was neutralized with hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to give 9.0 g of the compound of formula (K-5) below. White crystal of matter (K-5)).

[Synthesis Example 9]

In the same manner as in Synthesis Example 8, except that 110.9 g of 1-iodo-4,4,4-trifluorobutane was used instead of 1-bromopentane in Synthesis Example 8, 9.2 g of the following formula (K) was obtained. -6) White crystal of the compound (specific cinnamic acid derivative (K-6)) shown.

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

[Synthesis Example 10]

In a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane having an epoxy group obtained in the above Synthesis Example 1, 26 g of methyl isobutyl ketone, and 3 g of the specific cinnamic acid derivative obtained in the above Synthesis Example 4 (K-) were added. 1) and 0.10 g of UCAT 18X (trade name: quaternary ammonium salt manufactured by San-Apro Co., Ltd.), and stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was again precipitated with methanol, and the solvent was poured into ethyl acetate to give a solution. After the mixture was washed three times with water, the solvent was distilled off to obtain 6.3 g of a photo-aligned polyorganosiloxane compound (S-1). It is a white powder. The mass average molecular weight Mw of the photo-aligned polyorganosiloxane compound (S-1) was 3,500.

[Synthesis Example 11]

In the same manner as in Synthesis Example 10 except that 3 g of the specific cinnamic acid derivative (K-2) obtained in Synthesis Example 5 was used instead of the above K-1, 7.0 g of a photo-aligned polyorganosiloxane compound (S-2) was obtained. White powder. The mass-aligned polyorganosiloxane compound (S-2) had a mass average molecular weight Mw of 4,900.

[Synthesis Example 12]

In the same manner as in Synthesis Example 10 except that 4 g of the specific cinnamic acid derivative (K-3) obtained in Synthesis Example 6 was used instead of the above K-1, 10 g of a photo-aligned polyorganosiloxane compound (S-3) was obtained. White powder. The mass-aligned polyorganosiloxane compound (S-3) had a mass average molecular weight Mw of 5,000.

[Synthesis Example 13]

10 g of a photo-alignment polyorganosiloxane compound (S-4) was obtained in the same manner as in Synthesis Example 10 except that the specific cinnamic acid derivative (K-4) obtained in Synthesis Example 7 was used instead of the above K-1. White powder. The mass-aligned polyorganosiloxane compound (S-4) had a mass average molecular weight Mw of 4,200.

[Synthesis Example 14]

In the same manner as in Synthesis Example 10 except that 3 g of the specific cinnamic acid derivative (K-5) obtained in Synthesis Example 8 was used instead of the above K-1, 10 g of a photo-aligned polyorganosiloxane compound (S-5) was obtained. White powder. The mass-aligned polyorganosiloxane compound (S-5) had a mass average molecular weight Mw of 4,200.

[Synthesis Example 15]

To a 200 mL three-necked flask, 5.0 g of the polyorganosiloxane having an epoxy group, 46.4 g of methyl isobutyl ketone obtained in the above Synthesis Example 1, and 5.3 g of the specific cinnamic acid derivative obtained in Synthesis Example 9 (K) were added. -6) (corresponding to a ruthenium atom of a polyorganosiloxane having an epoxy group, corresponding to 50 mol%), 1.08 g of a compound represented by the following formula as a photosensitizing compound (relative to having an epoxy group) The ruthenium atom of the polyorganosiloxane of the group corresponds to 20 mol%) and 0.10 g of tetrabutylammonium bromide, and the mixture was stirred at 80 ° C for 12 hours to carry out a reaction. After completion of the reaction, the precipitate was again precipitated with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. After washing the solution three times with water, the solvent was distilled off to obtain 2.8 g of a photo-aligned polyorganosiloxane compound (S-6). , as a white powder. The mass-aligned polyorganosiloxane compound (S-6) had a mass average molecular weight Mw of 12,500.

[Synthesis Example 16]

The same procedure as in Synthesis Example 10 was carried out except that 5 g of lauric acid was used. As a result, 11 g of a white powder of a photo-alignment polyorganosiloxane compound (S-7) was obtained. The mass average molecular weight Mw of the photo-aligned polyorganosiloxane compound (S-7) was 6,000.

<[B] Synthesis of a compound containing an ester structure>

The ester-containing compound (B-1-1) was synthesized according to the following scheme.

[Synthesis Example 17]

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

<Synthesis of polylysine>

[Synthesis Example 18]

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

[Synthesis Example 19]

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

[Synthesis Example 20]

To be tetracarboxylic dianhydride 109 g (0.50 mol) of pyromellitic dianhydride and 98 g (0.50 mol) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and as a diamine compound 200 g (1.0 mol) of 4,4'-diaminodiphenyl ether was dissolved in 2,290 g of N-methyl-2-pyrrolidone, and after reacting at 40 ° C for 3 hours, 1,350 g of N-A was added. Base-2-pyrrolidone gave about 3,590 g of a solution containing 10% by mass of poly-proline (PA-3) (the amount of poly-proline was 359 g in mass).

[Synthesis Example 21]

By the following formula (RA-2) having 10g (0.022 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride and 5 g (0.022 mol) of diamine as photodimerity -1-1) The compound shown is reacted to give polylysine (RPA-1).

<Synthesis of Polyimine>

[Synthesis Example 22]

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

<Preparation of Composition for Organic Semiconductor Orientation>

[Example 1]

100 parts by mass of the photo-aligned polyorganosiloxane compound obtained in the above Synthesis Example 10 was dissolved in a solvent having a composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (quality ratio). -1) A solution having a solid concentration of 4.0% by mass was formed. This solution was filtered through a filter having a pore size of 1 μm to prepare an organic semiconductor alignment composition (A-1).

[Examples 2 to 5]

Various organic semiconductor alignment compositions (A-2) to (A-5) were prepared in the same manner as in Example 1 by changing the photo-alignment polyorganosiloxane compound. Further, in Example 4, 5 parts by mass of the ester-containing compound (B-1-1) obtained in Synthesis Example 17 was further added to 100 parts by mass of the photo-aligned polyorganosiloxane compound to prepare an organic semiconductor alignment. Use the composition. Their ratios are shown in Table 2.

[Comparative Example 1]

13.1 g of poly(2-hydroxyethyl methacrylate) was dissolved by heating in 50 mL of N-methyl-2-pyrrolidone, and after cooling to room temperature, 10 mL of pyridine was added. 17.0 g of cinnabarin chloride was added thereto and stirred for 8 hours. The reaction mixture was diluted with N-methyl-2-pyrrolidone, and then 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 form a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (quality ratio), solid content concentration 4.0% by mass The solution. This solution was filtered through a filter having a pore size of 1 μm to prepare a composition (CA-1).

[Comparative Example 2]

Adding 1.00 g of 4-(2-methylpropenyloxyethoxy)azobenzene and 0.01 g of 2,2'-azobis(isobutyronitrile) and 2.00 g of dry benzene to the ampoule, row After the gas was sealed, the tube was sealed and injected into methanol to obtain a precipitate of a polymer compound. After filtering this, the precipitate was again dissolved in benzene, and the operation of reprecipitation with methanol and filtration was repeated twice, followed by drying. N-methyl-2-pyrrolidone and butyl cellosolve were added thereto to form a solvent composition of N-methyl-2-pyrrolidone: butyl cellosolve = 50:50 (mass ratio), solid concentration 4.0% by mass The solution. This solution was filtered through a filter having a pore size of 1 μm to prepare a composition (CA-2).

<Formation of Organic Semiconductor Alignment Film and Manufacture of Organic Semiconductor Element>

A gate electrode having a thickness of 20 nm was formed on the glass substrate by a vacuum evaporation method using Al as an electrode material. Thereafter, the polyamic acid (PA-1) prepared in Synthesis Example 18 was applied by a spin coater, and internally heated in an oven substituted with nitrogen at 200 ° C for 1 hour (baking) to form a film thickness of 0.2 μm. Insulating film. Next, the organic semiconductor alignment composition (A-1) prepared in Example 1 was applied onto the insulating film by a spin coater, and prebaked on a hot plate at 80 ° C for 1 minute, and then placed in an internal nitrogen-substituted oven. The film was heated at 200 ° C for 1 hour (post-baking) to form a coating film having a film thickness of 0.1 μm. The solid content concentration of the organic semiconductor alignment composition (A-1) was 4.0% by mass, so that the film thickness after the formation was 0.1 μm, the number of revolutions of the spinner was 2000 rpm, and the organic semiconductor alignment composition (A-1). Next, on the surface of the coating film, a linearly polarized ultraviolet ray containing a bright line of 313 nm was vertically irradiated from the substrate normal line using an Hg-Xe lamp and a Glan-Taylor prism to form an organic semiconductor alignment film. The amount of light irradiation necessary for the alignment of the photo-alignment group in the coating film formed at this time was measured, and it was used as a sensitivity index of photo-alignment. Further, the alignment of the photo-alignment group was confirmed using a polarizing microscope.

Next, in the organic semiconductor alignment film, a source and a drain were formed by gold vapor deposition to have a channel length of 30 μm and a channel width of 50 μm. Next, in order to cover the above two electrodes, a film thickness of modified pentacene is formed by vapor deposition 700. Organic semiconductor molecular film, manufacturing a top gate type organic semiconductor element.

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

<Evaluation of Organic Semiconductor Components>

(1) Evaluation of initial carrier mobility

The initial carrier mobility of the front gate type organic semiconductor device manufactured in the above procedure was measured using a semiconductor parameter analyzer (Semiconductor parameter analyzer HP4155a, manufactured by Hewlett Packard Co., Ltd.).

(2) Evaluation of carrier mobility after heating

The organic semiconductor element was placed under heating, and the mobility of the carrier after the heating was measured to evaluate the stability to heat. Specifically, the front-gate organic semiconductor device manufactured in the above-described step was heated in an oven set at 70 ° C for 500 hours, and then measured in the same manner as in the above "(1) Evaluation of initial carrier mobility]. After the carrier mobility. The evaluation results are shown in Table 2. The maintenance rate of the carrier mobility after heating is also shown in Table 2.

As is apparent from the results of Table 2, when the organic semiconductor alignment film of the examples 1 to 5 was used to produce an organic semiconductor alignment film, the amount of light irradiation necessary for light alignment was extremely low, and the sensitivity of light alignment was good. Further, the organic semiconductor element having the alignment film can achieve high carrier mobility, and the organic semiconductor element can maintain the initial carrier mobility at a high ratio even after being heated, thereby obtaining excellent heat resistance. . On the other hand, the alignment film produced by using the composition of Comparative Example 1 has a good sensitivity to photo-alignment and a carrier mobility of the semiconductor element, but the carrier mobility after heating is about half, indicating that the heat resistance is poor. As a result of using the alignment film produced by the composition of Comparative Example 2, the amount of light irradiation of the light alignment of 20,000 J/m ² was also required, and the carrier mobility was also lower than half of the carrier mobility of the organic semiconductor element of the example. value.

<Preparation of an organic semiconductor alignment composition having an insulating property>

[Embodiment 6]

In the above Synthesis Example 17, a solution containing polyglycine (PA-1) was obtained, and the amount of the polylysine (PA-1) contained therein was adjusted to be 1,000 parts by mass, and 100 parts by mass of the above Synthesis Example 10 was added thereto. The obtained photo-aligned polyorganosiloxane compound (S-1) is then added with N-methyl-2-pyrrolidone and butyl cellosolve to form a solvent to form N-methyl-2-pyrrolidone: butyl cellosolve A solution of 50:50 (mass ratio) and a solid concentration of 3.0% by mass. This solution was filtered through a filter having a pore size of 1 μm to prepare an organic semiconductor alignment composition (A-6).

[Examples 7 to 14]

Various organic semiconductor alignment compositions (A-7) to (A-14) are prepared by changing the combination of a photo-alignment polyorganosiloxane compound, poly-proline, and polyimine. These are shown in Table 2. Further, the photo-aligned polyorganosiloxane compounds (S-1) and (S-7) in Example 7 were each added in an amount of 50 parts by mass, and in Example 14, the polyamine contained in the above Synthesis Example 20 was used. The solution of the acid (PA-3) is equivalent to 2,000 parts by mass in terms of polyamine acid (PA-3).

[Comparative Example 3]

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

[Comparative Example 4]

A composition (CA-4) was prepared in the same manner as in Example 6 except that the photo-aligned polyorganosiloxane compound was not added, and poly-proline (PA-2) obtained in Synthesis Example 19 was used as the polyamic acid.

[Comparative Example 5]

A composition (CA-5) was prepared in the same manner as in Example 6 except that the photo-aligned polyorganosiloxane compound was not added, and poly-proline (RPA-1) obtained in Synthesis Example 21 was used as the polyamic acid.

[Comparative Example 6]

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

<Formation of Insulating Organic Semiconductor Alignment Film and Manufacture of Organic Semiconductor Element>

A gate electrode having a thickness of 20 nm was formed on the glass substrate by vacuum evaporation using Al. Then, the organic semiconductor alignment composition (A-6) prepared in Example 6 was applied by a spin coater, prebaked by a hot plate at 80 ° C for 1 minute, and then internally placed in an oven purged with nitrogen at 200 ° C. The film was heated for 1 hour (post-baking) to form a coating film having a film thickness of 0.2 μm. In order to form a film thickness of 0.2 μm, the number of revolutions of the spinner was 2000 rpm, and the solid content concentration of the alignment film solvent was 4%. Next, on the surface of the coating film, a linear polarized ultraviolet ray of 1,000 J/m ² containing a bright line of 13 nm was vertically irradiated from the substrate normal line using an Hg-Xe lamp and a Glan-Taylor prism to form an organic semiconductor alignment film.

Next, a source and a drain were formed in the organic semiconductor alignment film by gold vapor deposition to have a channel length of 30 μm and a channel width of 50 μm. Next, in order to cover the above two electrodes, a film thickness 700 of the modified pentacene is formed by an evaporation method. An organic semiconductor molecular film that produces a front gate type organic semiconductor element.

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

<Evaluation of Organic Semiconductor Components>

(1) Evaluation of volume specific resistance (insulation)

Using a tantalum wafer as a substrate, the organic semiconductor alignment composition (A-6) was applied by a spin coater, prebaked for 1 minute with a hot plate at 80 ° C, and then heated at 200 ° C in an internal nitrogen-substituted oven. One hour (prebaking), a coating film having a film thickness of 0.2 μm was formed. The solvent and solid content of the alignment film were adjusted to 4% in order to make the film thickness after formation 0.2 μm and the number of revolutions of the spin coater to 2000 rpm. Next, an Hg-Xe lamp and a Glan-Taylor prism were used on the surface of the coating film, and a linearly polarized ultraviolet ray of 1,000 J/m ² containing a bright line of 13 nm was vertically irradiated from the substrate normal to form an organic semiconductor alignment film. On the surface of the alignment film, Al was vapor-deposited as an upper electrode to form a substrate for measuring the film specific resistance. In the same measurement substrate, a ruthenium wafer was used as a lower electrode, an Al electrode was used as an upper electrode, a voltage of 1 V was applied, and a current was measured by an electrometer (R12706A manufactured by Advantest Co., Ltd.) to calculate a specific resistance.

(2) Evaluation of carrier mobility

The front gate type organic semiconductor element manufactured in the above procedure was measured for carrier mobility using a semiconductor parameter analyzer (Semiconductor parameter analyzer HP4155a, manufactured by Hewlett Packard Co., Ltd.).

As is clear from the results of Table 3, the organic semiconductor alignment film produced by using the composition for organic semiconductor alignment of Examples 6 to 14 is excellent in insulation property, and the organic semiconductor element having the alignment film can achieve extremely high carrier mobility. On the other hand, the insulating film produced using the compositions of Comparative Examples 3 and 4 has high insulating property, but since there is no photo-alignment group in the insulating film molecule, the carrier mobility of the semiconductor element is lowered to the tenth of the embodiment. one. The semiconductor element having the insulating film produced using the composition of Comparative Example 5 has a diamine structure derived from photo-alignment, or a high carrier mobility can be obtained, but the insulating property is lowered. The insulating film produced using the composition of Comparative Example 6 having no polyorganosiloxane skeleton had a low resistivity of one or more digits and poor insulating properties.

<Evaluation of the existence distribution of a specific cinnamic acid derivative in an organic semiconductor alignment film>

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

Using a TOF-SIMS measuring device manufactured by ULVAC-PHI, a Bi ₃ ⁺⁺ cluster ion with an accelerating voltage of 25 kV was used as a primary ion source, with an ion current of 0.05 pA, a measurement field of 100 μm, and a measurement mass range of 0 to 1,850 amu. The C ₆₀ sputtering and TOF-SIMS analysis were repeated on the surface of the coating film formed as described above, and the measurement was performed until indium ions from ITO were detected, and the time from the surface of the coating film to the depth of 80 nm was examined when the indium ions were detected. The composition distribution in the thickness direction of the coating film. A graph showing the distribution of the segments of m/z = 231 at this time is shown in Fig. 3 (presence distribution) and Fig. 4 (accumulated value). In addition, the graphs shown in these figures are values obtained by dividing the number of calculations of the segment at each depth by the noise level.

It is considered that the above fragment having m/z = 231 corresponds to a fragment represented by the following formula derived from the cinnamic acid derivative (K-6). Therefore, from the results of FIG. 3, it is presumed that in the coating film formed in the present embodiment, the group derived from the specific cinnamic acid derivative is present on the surface of the coating film at the highest concentration, and is biased from the surface to the thickness of 20%. Range (up to 30% range).

Industrial availability

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

Further, when the organic semiconductor alignment composition of the present invention containing a photoalignment polyorganosiloxane compound and polyglycolic acid and/or polyimine is used, the obtained organic semiconductor alignment film has, in addition to the above properties, It is suitable for use in organic semiconductor elements and the like because of its high insulating properties.

1. . . Organic semiconductor component

2. . . Substrate

3,11. . . Gate electrode

4,12. . . Gate insulating film

5. . . Oriented film for organic semiconductor

6,13. . . Source electrode

7,14. . . Bipolar electrode

8,15. . . Organic semiconductor layer

9. . . Organic semiconductor component

10. . . Substrate

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

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

Fig. 3 is a view showing the distribution of the presence of a fragment of m/z = 231 observed in the film thickness direction by the TOF-SIMS in the fourteenth embodiment.

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

Claims (11)

An organic semiconductor alignment composition which is an organic semiconductor alignment composition for forming an insulating alignment film for anisotropic alignment of an organic semiconductor molecule, comprising [A] having a photoalignment group in a side chain a polyorganosiloxane compound of the group, and at least one polymer selected from the group consisting of poly(prolyl) and polyamidiamine, wherein the photo-alignment group is a group having a cinnamic acid structure. And the group having a cinnamic acid structure is at least one selected from the group consisting of a group derived from a compound represented by the following formula (1) and a group derived from a compound represented by the following formula (2); In the formula (1), R ₁ is a part of a hydrogen atom extending a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group, and a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group. Or all of them may be substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms having a fluorine atom as a substituent, a fluorine atom or a cyano group, and R ₂ is a single bond or carbon. An alkyl group having 1 to 3 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 R ₃ may be the same as or a different one, and 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 phenyl group or a cyclohexyl group, and the phenyl group or the cyclohexyl group is stretched. A part or all of the hydrogen atom may be substituted by a chain or cyclic alkyl group having 1 to 10 carbon atoms, a chain or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group. R ₅ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-, and c is an integer of 1 to 3. When c is 2 or more, R ₄ and R ₅ may be respectively The same or different, R ₆ is a fluorine atom or a cyano group , d is an integer from 0 to 4, R ₇ is an oxygen atom, -COO-* or -OCO-* (wherein, in the above, a linkage with "*" and R _{8 are} attached), and R ₈ is a divalent An aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -* (wherein, in the above, a "*" linkage and a carboxyl linkage), f and g are integers from 1 to 10, respectively, and e is an integer from 0 to 3. The organic semiconductor alignment composition according to claim 1, wherein the polyorganosiloxane compound having a photo-alignment group is selected from the group consisting of polyorganosiloxane having an epoxy group, hydrolyzate thereof, and At least one of the group consisting of the condensate of the hydrolyzate, and at least one selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2). The organic semiconductor alignment composition according to the second aspect of the invention, wherein the epoxy group is represented by the following formula (X ₁ -1) or (X ₁ -2), In the formula (X ₁ -1), A is an oxygen atom or a single bond, h is an integer of 1 to 3, and i is an integer of 0 to 6, wherein, when i is 0, A is a single bond, and the formula (X ₁ In -2), j is an integer from 1 to 6, and in the formulas (X ₁ -1) and (X ₁ -2), "*" indicates a connection key. The organic semiconductor alignment composition according to any one of claims 1 to 3, further comprising [B] a acetal ester structure having two or more carboxylic acids, a ketal ester structure of a carboxylic acid, a carboxylic acid A compound of at least one structure selected from the group consisting of a 1-alkylcycloalkyl ester structure and a tertiary butyl ester structure of a carboxylic acid. The organic semiconductor alignment composition according to claim 1, wherein the polyamic acid and the polyimine are selected from the group consisting of an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride. A reaction product of at least one tetracarboxylic dianhydride, at least one diamine selected from the group consisting of an alicyclic diamine and an aromatic diamine. An organic semiconductor alignment film formed by the composition for an organic semiconductor alignment according to any one of claims 1 to 5. An organic semiconductor alignment film in which a group having a cinnamic acid structure is in a range from 30% to a film thickness, and the above group having a cinnamic acid structure is a compound derived from the following formula (1) At least one selected from the group consisting of a group derived from a compound represented by the following formula (2); In the formula (1), R ₁ is a part of a hydrogen atom extending a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group, and a phenyl group, a biphenyl group, a terphenyl group or a cyclohexyl group. Or all of them may be substituted by an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms having a fluorine atom as a substituent, a fluorine atom or a cyano group, and R ₂ is a single bond or carbon. An alkyl group having 1 to 3 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 R ₃ may be the same as or a different one, and 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 phenyl group or a cyclohexyl group, and the phenyl group or the cyclohexyl group is stretched. A part or all of the hydrogen atom may be substituted by a chain or cyclic alkyl group having 1 to 10 carbon atoms, a chain or cyclic alkoxy group having 1 to 10 carbon atoms, a fluorine atom or a cyano group. R ₅ is a single bond, an alkylene group having 1 to 3 carbon atoms, an oxygen atom, a sulfur atom or -NH-, and c is an integer of 1 to 3. When c is 2 or more, R ₄ and R ₅ may be respectively The same or different, R ₆ is a fluorine atom or a cyano group , d is an integer from 0 to 4, R ₇ is an oxygen atom, -COO-* or -OCO-* (wherein, in the above, a linkage with "*" and R _{8 are} attached), and R ₈ is a divalent An aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R ₉ is a single bond, -OCO-(CH ₂ ) _f -* or -O(CH ₂ ) _g -* (wherein, in the above, a "*" linkage and a carboxyl linkage), f and g are integers from 1 to 10, respectively, and e is an integer from 0 to 3. An organic semiconductor device comprising: a gate formed on a substrate, an insulating film formed over the gate, and the organic semiconductor alignment according to any one of claims 1 to 5 on the insulating film An organic semiconductor alignment film formed of the composition, a source and a drain formed on the organic semiconductor alignment film, and an organic semiconductor layer formed at least between the source and the drain. A method of manufacturing an organic semiconductor device, comprising: an insulating film forming step of forming an insulating film to cover a gate formed on a substrate; and the insulating film, by any one of claims 1 to 5 a coating film forming step of forming a coating film by the organic semiconductor alignment composition; an electrode forming step of forming a source and a drain on the coating film; and forming an organic semiconductor layer between at least the source and the drain The organic semiconductor layer forming step further includes the step of irradiating the coating film with linearly polarized light to form an organic semiconductor alignment film before the organic semiconductor layer forming step. An organic semiconductor device comprising: a gate electrode formed on a substrate, an organic semiconductor alignment film for covering the gate electrode formed by the organic semiconductor alignment composition of claim 1 or 5, A source and a drain formed on the organic semiconductor alignment film, and an organic semiconductor layer formed at least between the source and the drain. A method of producing an organic semiconductor device, comprising: a coating film forming step of forming a coating film by using an organic semiconductor alignment composition according to claim 1 or 5 to cover a gate electrode formed on the substrate; An electrode forming step of forming a source and a drain; and an organic semiconductor layer forming step of forming an organic semiconductor layer between the source and the drain; and further irradiating the coating film with a straight line before the step of forming the organic semiconductor layer The step of deflecting light to form an organic semiconductor alignment film.