JP2015198115A - Thermosetting or photocurable composition, and insulating film and thin-film transistor each using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting or photocurable composition enabling stability in TFT characteristics to be improved by improving easiness to be applied of an organic semiconductor material, and to provide an insulating film and a thin-film transistor each using the thermosetting or photocurable composition.SOLUTION: The thermosetting and photocurable composition is provided which contains a polyorganosiloxane compound (AP) at least having a structure unit A and a structure unit B represented by the following general formula (I), an insulating film obtained by hardening the composition, and a thin-film transistor having the insulating film as a gate insulating layer are also provided. In the formula, R-Reach and independently represent 1-4C alkyl groups or phenyl groups, and Lrepresents a single bond or a bivalent coupling group, and Rrepresents a hetero ring group with the exception of a cyanuric ring group, of three or more C and at least one of O, N and S. In addition, a and b are each 1-99 mol%.

Description

  The present invention relates to a thermosetting or photocurable composition, and an insulating film and a thin film transistor using the composition.

  A display device such as a liquid crystal display, an organic EL display, and an electrophoretic display includes a semiconductor element such as a thin film transistor (TFT).

The TFT has a gate electrode, a gate insulating layer, a source electrode, and a drain electrode, and the source electrode and the drain electrode are connected by a semiconductor layer. In such a TFT, when a voltage is applied to the gate electrode, a current flow channel (channel) is formed in the vicinity of the interface between the semiconductor layer between the source electrode and the drain electrode and the gate insulating layer adjacent to the semiconductor layer. Is done. That is, the current flowing between the source electrode and the drain electrode is controlled according to the input voltage applied to the gate electrode.
Thus, the gate insulating layer provided adjacent to the semiconductor layer has a function of forming a current flow path together with the semiconductor layer. Therefore, not only the semiconductor layer but also the gate insulating layer and the material forming the gate insulating layer are important for improving the performance of the TFT.

  As a material for forming the gate insulating layer, a composition containing a polyorganosiloxane compound is known. For example, Patent Document 1 describes a curable composition containing a modified polyorganosiloxane compound having a specific ring structure such as cyanuric acid. In addition, Patent Documents 2 and 3 describe materials or photocurable compositions containing a polyorganosiloxane compound having an alkyl group or an aryl group.

JP 2010-285518 A International Publication No. 2009/116373 Pamphlet JP 2011-187558 A

However, when the gate insulating layer is formed using a composition containing a conventional polyorganosiloxane compound, the organic semiconductor material for forming the organic semiconductor layer may not be uniformly coated on the gate insulating layer (for the gate insulating layer). The applicability of organic semiconductor materials is poor. Accordingly, the film quality of the formed semiconductor layer is deteriorated, and a thin film transistor having such a gate insulating layer and a semiconductor layer cannot exhibit sufficient TFT characteristics. In addition, TFT characteristics, for example, carrier mobility, in a moist heat environment decrease with time, and the wet heat stability of the TFT characteristics is not sufficient.
Here, the moist heat environment is assumed to be an environment in which the thin film transistor is used.

  The present invention relates to a heat or photocurable composition that improves the coatability of an organic semiconductor material and improves the wet heat stability of TFT characteristics, and an insulating film and a thin film transistor using the heat or photocurable composition. The issue is to provide.

  The present inventors have studied a curable composition containing a polyorganosiloxane compound for forming an insulating layer. As a result, it has been found that by introducing a specific heterocycle that does not affect the curing reaction into the polyorganosiloxane compound, the coating property of the organic semiconductor material on the cured product of this curable composition can be improved. Moreover, it has also been found that when a cured product of this curable composition is provided as a gate insulating layer, the wet heat stability of TFT characteristics is improved. The present invention has been completed based on these findings.

The above problem has been solved by the following means.
[1] A heat or photocurable composition containing a polyorganosiloxane compound (AP) having at least a structural unit A and a structural unit B represented by the following general formula (I).

In formula ^(I), represents an alkyl group or a phenyl group having 1 to 4 carbon atoms R 1, ^{R 2} and ^{R 3} each independently. L ¹ represents a single bond or a divalent linking group. R ^x represents an aliphatic or aromatic heterocyclic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and having 3 or more carbon atoms. However, ^Rx excludes a cyanuric ring group. a and b represent the content of the structural unit A and the structural unit B in the polyorganosiloxane compound (AP), respectively, and are 1 to 99 mol%.

[2] The heat or photocurable composition according to [1], wherein the polyorganosiloxane compound (AP) has a structural unit A, a structural unit B, and a structural unit C represented by the following general formula (II).

In the general formula ^{(II), R 1, R} 2, R 3, L 1 and ^{R x} are respectively the same as ^{R 1, R 2, R 3} , L 1 and ^{R x} in formula (I). R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms or a phenyl group. L ² represents a single bond or a divalent linking group, and R ^y represents a radical or a cation polymerizable functional group. a, b, and c represent the content of the structural unit A, the structural unit B, and the structural unit C in the polyorganosiloxane compound (AP), respectively, and are 1 to 98 mol%.

[3] The heat or photocurable composition according to [1] or [2], wherein R ^x is a nitrogen-containing aliphatic heterocycle or a nitrogen-containing aromatic heterocycle.
[4] ^Rx is a piperidine ring group, piperazine ring group, morpholine ring group, quinuclidine ring group, pyrrolidine ring group, azetidine ring group, azetidin-2-one ring group, aziridine ring group, tropane ring group, pyrrole ring group , Furan ring group, thiophene ring group, imidazole ring group, pyrazole ring group, 1,2,3-triazole ring group, 1,2,4-triazole ring group, tetrazole ring group, oxazole ring group, isoxazole ring group, Thiazole ring group, isothiazole ring group, thiadiazole ring group, phosphole ring group, pyridine ring group, pyrimidine ring group, pyridazine ring group, pyrazine ring group, 1,2,3-triazine ring group, 1,2,4-triazine Ring group, quinoline ring group, isoquinoline ring group, quinazoline ring group, phthalazine ring group, pteridine ring group, coumarin ring group, chromone ring group, 1,4- Benzodiazepine ring group, indole ring group, benzimidazole ring group, benzotriazole ring group, benzofuran ring group, purine ring group, acridine ring group, phenoxazine ring group, phenothiazine ring group, benzothiadiazole ring group, isobenzofuran ring group, iso Indole ring group, benzo (b) thiophene ring group, benzo (c) thiophene ring group, benzophosphole ring group, indazole ring group, benzoxazole ring group, benzoisoxazole ring group, benzothiazole ring group, quinoxaline ring group, The heat or photocurable composition according to any one of [1] to [3], which is at least one selected from the group consisting of cinnoline ring groups.
[5] The thermal or photocurable composition according to any one of [1] to [4], wherein ^Ry is a radical polymerizable functional group.
[6] The heat or photocurable composition according to any one of [1] to [5], wherein ^Ry is a (meth) acryloyloxy group or a styryl group.
[7] At least a part of the polyorganopolysiloxane compound (AP) has a hydrosilyl group, the hydrosilyl group of the polyorganopolysiloxane compound, and the compound (MC) having two or more alkenyl groups that do not exhibit radical polymerizability; The heat or photocurable composition according to any one of [1] to [6], which contains a modified polyorganosiloxane compound (mAP) obtained by reaction of
[8] The heat- or photocurable composition according to [7], wherein the alkenyl group that does not exhibit radical polymerizability is a vinyl group or an allyl group.
[9] The heat or photocurable composition according to [7] or [8], wherein the compound (MC) having two or more alkenyl groups that do not exhibit radical polymerizability is a polyfunctional allyl compound.
[10] The heat- or photo-curable composition according to any one of [1] to [9], which includes a compound (B) having a radical or cation polymerizable functional group.
[11] The heat or photocurable composition according to [10], wherein the compound (B) is a compound having a radical polymerizable functional group.
[12] The heat or photocurable composition according to any one of [1] to [11], which contains a heat or photopolymerization initiator.
[13] An insulating film obtained by curing the heat or photocurable composition according to any one of [1] to [12].
[14] A thin film transistor having the insulating film according to [13] as a gate insulating layer.
[15] The thin film transistor according to [14], wherein the gate insulating layer is provided between the gate electrode and the semiconductor layer provided on the gate electrode.

  In the present specification, when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents, etc. are defined simultaneously, each substituent, etc. Means the same or different. The same applies to the definition of the number of substituents and the like. Further, when there are repetitions of a plurality of partial structures represented by the same indication in the formula, each partial structure or repeating unit may be the same or different. Even when not particularly specified, when a plurality of substituents and the like are close (particularly adjacent), they may be connected to each other or condensed to form a ring.

  In this specification, about the display of a compound, it uses in the meaning containing the salt and its ion besides the compound itself. In addition, it means that a part of the structure is changed as long as the desired effect is achieved.

  In the present specification, a group that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent as long as a desired effect is achieved. This is also synonymous for compounds that do not specify substitution / non-substitution.

  In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

The heat or photocurable composition of the present invention and the insulating film formed by curing the composition can improve the coating property of the organic semiconductor material and improve the wet heat stability of the TFT characteristics.
Moreover, the thin film transistor of the present invention has high TFT characteristics and excellent wet heat stability.

It is a figure which shows typically the structure of the organic thin-film transistor which is an example of the semiconductor element of this invention.

[Heat or photo-curable composition]
The heat or photocurable composition of the present invention (referred to as the curable composition of the present invention) comprises a polyorganosiloxane compound (AP) having at least a structural unit A and a structural unit B represented by the following general formula (I). contains. Preferably, it contains a compound (B) having a radical or cationic polymerizable functional group.
The curable composition of the present invention is cured by heat, light or heat and light to form a cured product.

[Polyorganosiloxane compound (AP)]
The polyorganosiloxane compound (AP) used in the present invention has a structural unit A and a structural unit B represented by the following general formula (I).

In general formula (I), R < ¹ >, R < ² > and R < ³ > represent a C1-C4 alkyl group or a phenyl group each independently. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. This alkyl group may be linear or branched. As for carbon number of an alkyl group, 1 or 2 is preferable. R ¹ , R ² and R ³ are each independently preferably a methyl group or a phenyl group, and more preferably a methyl group.

L ¹ represents a single bond or a divalent linking group.
As a bivalent coupling group, it is synonymous with the coupling group L mentioned later, and the bivalent coupling group represented by either of the following general formula (L-1)-(L-25), or the following general formula A divalent linking group formed by bonding two or more divalent linking groups represented by any of (L-1) to (L-25) is preferable. In each general formula, a wavy line part represents a bonding position with a silicon atom or a bonding position with * in the general formulas (L-1) to (L-25). * Represents a bonding position with R ^x or a bonding position with a wavy line part of the general formulas (L-1) to (L-25).
Examples of the substituent that the divalent linking group may have include the substituent T described later.

Among them, ^{L 1} is the general formula (L-1), (L -4), (L-7), (L-9), (L-10), 2 -valent represented by (L-13) Or a divalent linking group formed by bonding one or more of these linking groups is more preferred.
L ¹ is a divalent linking group formed by bonding two or more general formulas (L-1), one or more general formulas (L-1), and one or more general formulas (L-4). A divalent linking group formed by bonding one or more general formulas (L-1) and one or more general formulas (L-7), one or more A divalent linking group formed by combining the general formula (L-1) and one general formula (L-9) is more preferable.

When L ¹ is a linking group formed by bonding a divalent linking group represented by any ^one of the general formulas (L-1) to (L-25), the general formulas (L-1) to (L The number of bonds of the divalent linking group represented by any one of -25) is preferably 2-15, more preferably 2-10, and particularly preferably 2-4.

L ¹ is particularly preferably — (CH ₂ ) n— or — (CH ₂ ) n—O—C (═O) —. Here, n shows the integer of 2-4.

R ^x represents an aliphatic heterocyclic group or an aromatic heterocyclic group having at least one hetero atom of an oxygen atom, a nitrogen atom, and a sulfur atom and three or more carbon atoms as ring-constituting atoms.
The heterocyclic group of the aliphatic heterocyclic group or aromatic heterocyclic group is a nitrogen-containing aliphatic heterocyclic group containing at least a nitrogen atom as a ring-constituting atom or a nitrogen-containing aromatic heterocyclic group in terms of adhesion to the electrode. Preferably, a nitrogen-containing aromatic heterocycle is more preferable. When there are a plurality of heteroatoms as ring constituent atoms, the plurality of heteroatoms may be different or the same.
The number of heteroatoms constituting the heterocycle may be at least one, preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2. The number of carbon atoms as a ring-constituting atom may be 3 or more, and is appropriately determined according to the number of heteroatoms and the number of ring members. The number of carbon atoms is preferably 3-5. In addition, when R ^x has a plurality of heterocyclic groups, it is preferable to satisfy the number of ring constituent atoms for each.

  The heterocyclic ring serving as a heterocyclic group is preferably a 5- or 6-membered ring, and an aromatic carbocyclic ring, aromatic heterocyclic ring, aliphatic heterocyclic ring or alicyclic ring may be condensed. The condensed ring is preferably an aromatic carbocyclic ring, particularly preferably a benzene ring. The aromatic carbocyclic ring or alicyclic ring is preferably condensed on the main chain side of the polyorganosiloxane compound (AP). The number of rings to be condensed is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.

In the present invention, the heterocyclic group R ^x is a cyanuric ring group (triazine-2,4,6-triol ring and triazine-2,4,6-trione ring) and a triazine-2,4,6-triol ring. The alkyl substitution product is not included.

  The heterocyclic group may have a substituent. Examples of such a substituent T include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), and a halogen atom. , A hydroxyl group, an alkoxy group (preferably having 1 to 6 carbon atoms), a carboxyl group, an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an oxo group (═O) and a group formed by combining these groups (preferably total carbon Number 1-30, More preferably, total carbon number 1-15 is mentioned.

  Examples of the aliphatic heterocyclic group include, but are not limited to, for example, piperidine ring group, piperazine ring group, morpholine ring group, thiomorpholine ring group, quinuclidine ring group, pyrrolidine ring group, azetidine ring group, oxetane ring group, azetidine- A 2-one ring group, an aziridine ring group, and a tropane ring group are mentioned.

Although it does not specifically limit as an aromatic heterocyclic group, A 5-membered aromatic heterocyclic group, a 6-membered aromatic heterocyclic group, or a polycyclic aromatic heterocyclic group etc. are mentioned preferably.
Specific examples of the 5-membered aromatic heterocyclic group include pyrrole ring group, furan ring group, thiophene ring group, imidazole ring group, pyrazole ring group, 1,2,3-triazole ring group, 1,2, Examples include 4-triazole ring group, tetrazole ring group, oxazole ring group, isoxazole ring group, thiazole ring group, isothiazole ring group, thiadiazole ring group, and phosphole ring group.
The six-membered aromatic heterocyclic group includes nitrogen-containing pyridine ring group, pyrimidine ring group, pyridazine ring group, pyrazine ring group, 1,2,3-triazine ring group, 1,3,5-triazine ring group, etc. A heterocycle is mentioned.

  As the polycyclic aromatic heterocyclic group, quinoline ring group, isoquinoline ring group, quinazoline ring group, phthalazine ring group, pteridine ring group, coumarin ring group, chromone ring group, 1,4-benzodiazepine ring group, indole ring group, Benzimidazole ring group, benzotriazole ring group, benzofuran ring group, purine ring group, acridine ring group, phenoxazine ring group, phenothiazine ring group, benzothiadiazole ring group, isobenzofuran ring group, isoindole ring group, benzo (b) Examples include a thiophene ring group, a benzo (c) thiophene ring group, a benzophosphole ring group, an indazole ring group, a benzoxazole ring group, a benzoisoxazole ring group, a benzothiazole ring group, a quinoxaline ring group, and a cinnoline ring group.

  Examples of the heterocyclic group include pyridine ring group, 1,2,3-triazine ring group, 1,3,5-triazine ring group, benzotriazole ring group, benzothiazole ring group, benzimidazole ring group, benzo (b) thiophene. A ring group, a benzo (c) thiophene ring group, a benzoxazole ring group, and a benzothiadiazole ring group are preferable, and a benzotriazole ring group, a benzothiazole ring group, and a benzothiadiazole ring group are particularly preferable.

The bonding position of the heterocyclic group with the linking group L ¹ is not particularly limited, but is preferably an atom other than the ring constituent atom adjacent to the hetero atom. For example, when the ring-constituting atom bonded to the linking group L ¹ is the 1st position, the heteroatom is preferably in the 3rd or higher position.

When the polyorganosiloxane compound (AP) has a plurality of heterocyclic groups R ^x , the plurality of heterocyclic groups R ^x may be the same as or different from each other.
In addition, it is preferable that one R ^x is bonded to the linking group L ¹ . In the present invention, the number of bonds is not limited, and n (n is an integer of 2 or more) R ^x may be bonded to the linking group L ¹ . In this case, the side chain of the structural unit B is represented by “—L ^1- (R ^x ) n”, and L ¹ is a linking group of n.

  The polyorganosiloxane compound (AP) preferably has a structural unit A, a structural unit B, and a structural unit C represented by the following general formula (II).

In formula ^{(II), R 1, R} 2, R 3, L 1 and ^{R x} are each, the same meaning as ^{R 1, R 2, R 3} , L 1 and ^{R x} of formula (I), The preferred ones are the same.

R ⁴ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, has the same meaning as R ¹ , and preferred ones are also the same.
L ² represents a single bond or a divalent linking group, and has the same meaning as L ^{1 in} formula (I), and preferred ones are also the same.

R ^y represents a radical polymerizable functional group or a cationic polymerizable functional group, and is preferably a radical polymerizable functional group.
The radical polymerizable functional group is not particularly limited as long as it is a functional group that can be polymerized by radicals. For example, an ethylenically unsaturated bond capable of radical polymerization (radical polymerizable unsaturated double bond) or an ethylenically unsaturated bond. And a polymerizable group having. The polymerizable group having an ethylenically unsaturated bond may be any group as long as it has at least one ethylenically unsaturated bond, but is preferably a group having one ethylenically unsaturated bond.
Specifically, for example, a (meth) acrylic acid ester group ((meth) acryloyloxy group), an itaconic acid ester group (itaconoyloxy group), a crotonic acid ester group (crotonoyloxy group), an isocrotonic acid ester group ( Examples thereof include unsaturated carboxylic acid ester groups (unsaturated carbonoyloxy groups) such as (isocrotonoyloxy group) and maleic acid ester groups (malenoyloxy groups), styryl groups, acrylamide groups and vinyl ether groups. Of these, a (meth) acryloyloxy group and a styryl group are preferable.
This radical polymerizable functional group may have a substituent T.

The cationically polymerizable functional group is not particularly limited as long as it is a functional group that can be polymerized by a cation, and examples thereof include a group possessed by a cationically polymerizable compound described later. Specific examples include an epoxy group, an oxetanyl group, a vinyl ether group, and a cyclic lactone group.
The epoxy group and the oxetanyl group may be condensed with a ring such as an alicyclic ring. Preferred examples of such an epoxy group or oxetanyl group include the following groups, but the present invention is not limited thereto. In addition, in each of the following groups, the position at which the linking group L ² is bonded is not particularly limited.

As the cationically polymerizable functional group, an epoxy group and an oxetane group are preferable, and an epoxycyclohexyl group is more preferable.
The cationically polymerizable functional group may have a substituent T.

The polyorganosiloxane compound (AP) may have a structural unit or a repeating unit other than the above structural units A to C.
An example of such a structural unit is a structural unit D having a hydrosilyl (Si—H) group. The polyorganosiloxane compound (AP) having the structural unit D preferably has each structural unit represented by the following general formula (Ia) or (II-a).

In the general formula ^{(I-a), R 1} , R 2, R 3, L 1 and ^{R x} are respectively the same as ^{R 1, R 2, R 3} , L 1 and ^{R x} in formula (I). R ⁵ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and has the same meaning as R ¹ , and preferred ones are also the same.

In general formula (II-a), R ¹ , R ² , R ³ , R ⁴ , L ¹ , L ² , R ^x and R ^y are respectively R ¹ , R ² , R ^{3 in} general formula (II). , R ⁴ , L ¹ , L ² , R ^x and R ^y . R ⁵ is as described above.

At least a part of the organopolysiloxane compound (AP) has a hydrosilyl group (structural unit D), and this hydrosilyl group reacts with a compound (MC) having two or more alkenyl groups that do not exhibit radical polymerizability. The modified polyorganosiloxane compound (mAP) obtained in this way may be included. That is, the curable composition of the present invention comprises a modified polyorganosiloxane compound (mPA) obtained by reacting the hydrosilyl group of the organopolysiloxane compound (AP) with the compound (MC), and the organopolysiloxane compound (AP). ) May be included as at least a part of.
The modified polyorganosiloxane compound (mAP) is not uniquely determined by the compound (MC), the reaction conditions, the reaction ratio, etc. For example, the structural unit E formed by the addition reaction of the compound (MC) with the structural unit D And a network polymer formed by crosslinking the structural unit D using the compound (MC) as a crosslinking agent. This network polymer is a partial product that does not reach the target cross-linking with respect to the cured product of the heat- or photo-curable composition of the present invention (having the target cross-linking to function as an insulating film). It has cross-linking. Although partial bridge | crosslinking is not specifically limited, For example, it can prescribe | regulate with the content rate e of the structural unit E mentioned later.

The modified polyorganosiloxane compound (mAP) may be at least part of the polyorganosiloxane (AP), and the content of the modified polyorganosiloxane compound (mAP) in the polyorganosiloxane compound (AP) is not particularly limited. . For example, it is 10 to 100% by mass.
Although it does not specifically limit as polyorganosiloxane compound (AP) which has a hydrosilyl group, The compound represented by the said general formula (Ia) or (II-a), the commercial item mentioned later, etc. are mentioned.

  The alkenyl group is not particularly limited as long as it does not exhibit radical polymerizability and reacts with the structural unit D. Here, the “alkenyl group not exhibiting radical polymerizability” refers to an alkenyl group constituting a non-conjugated double bond monomer having a Q value of 0.2 or less. The Q value is a Q value of “Q, e-Scheme” proposed by Alfreey and Price as a measure for estimating the polymerization reactivity of the vinyl monomer. For a description of “Q, e-Scheme” and Q values of various monomers, the polymer handbook (2nd edition J. Brandrup, edited by EH Immergut) can be referred to. Also, the Q value can be estimated by experiment.

Examples of such an alkenyl group include an alkenyl group different from the polymerizable functional group represented by ^Ry , specifically, vinyl group, allyl group, methallyl group, 2-hydroxy-3- (allyloxy). Propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) Examples include an ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and vinyl ether group. From the viewpoint of reactivity, a vinyl group, an allyl group, a vinyl ether group and the like are preferable, and a vinyl group and an allyl group are particularly preferable.

As the compound (MC), for example, a polyfunctional allyl compound is preferably exemplified. Specifically, diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1,1,2, 2-tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohex Sandimethanol diallyl ether, triethylene glycol diallyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, bisphenol S Allyl ether, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantane, 1,3-bis (vinyloxy) adamantane, 1,3 , 5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, bisphenol A diallyl ether, 2 , 5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol allyl ether, Allylated polyphenyle Oxide, other, etc. are replaced with the allyl groups all glycidyl groups of known epoxy resins.
In addition, the following polyfunctional allyl compounds are also preferred.

  Further, the organic polymer compound described in paragraph [0081] of Patent Document 1 and the polyorganosiloxane compound described in paragraph [0079] of the same publication, a cyanuric ring group substituted with a substituent containing an alkenyl group (for example, mono (Allyl isocyanuric acid, diallyl isocyanuric acid, triallyl isocyanuric acid), and compounds having functional groups other than alkenyl groups. Although it does not specifically limit as groups other than an alkenyl group, For example, the said cation polymerizable functional group etc. are mentioned.

The modified polyorganosiloxane compound (mPA) is obtained by reacting the hydrosilyl group of the organopolysiloxane compound (AP) with the compound (MC).
In this hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst. Known hydrosilylation catalysts can be used without any particular limitation, but chloroplatinic acid, platinum olefin complexes, platinum vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.
The amount of the catalyst used is not particularly limited, but is preferably 10 ⁻⁸ mol or more, more preferably 10 ⁻⁶ mol or more, based on 1 mol of the alkenyl group in order to allow the hydrosilylation reaction to proceed rapidly. The amount is preferably 10 ⁻¹ mol or less, more preferably 10 ⁻² mol or less, relative to 1 mol of the alkenyl group.

In addition to the above catalyst, a cocatalyst may be used. Examples of the cocatalyst include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, acetylenes such as 2-hydroxy-2-methyl-1-butyne and 1-ethynyl-1-cyclohexanol. Examples thereof include alcohol compounds and sulfur compounds such as simple sulfur. The amount of the cocatalyst used is not particularly limited, but is preferably 10 ^-2 mol or more, more preferably 10 ^-1 mol or more with respect to 1 mol of the hydrosilylation catalyst, while preferably with respect to 1 mol of the alkenyl group. 10 ² mol, more preferably 10 mol or less.

  The reaction ratio between the organopolysiloxane compound (AP) and the compound (MC) is not particularly limited, but the total hydrosilyl group amount relative to the total alkenyl group amount is preferably 1 to 30, and preferably 1 to 15. .

  The reaction temperature is not particularly limited and can be appropriately set, but is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and preferably 200 ° C. or lower, more preferably 150 ° C. or lower. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  The reaction time and the pressure during the reaction can be appropriately set as necessary. In addition, oxygen can be used in the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. The oxygen volume concentration in the gas phase is preferably 0.1% or more, more preferably 1% or more, from the viewpoint that the effect of promoting the hydrosilylation reaction by addition of oxygen is observed.

  A solvent can also be used in the hydrosilylation reaction. The solvent is not particularly limited as long as the hydrosilylation reaction is not inhibited. For example, hydrocarbon solvents such as benzene, toluene, hexane, heptane, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, chloroform, methylene chloride, 1 And halogen solvents such as 2-dichloroethane. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

The polyorganosiloxane compound (AP) may be a random copolymer of the above structural units or a block copolymer.
Although the weight average molecular weight (Mw) of a polyorganosiloxane compound (AP) is not specifically limited, It is preferable that it is 1000-500000, It is more preferable that it is 1500-100000, It is further more preferable that it is 2000-80000.
In the present invention, Mw is, for example, HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm HD × 30.0 cm) as a column, and THF (eluent). Tetrahydrofuran) or NMP (N-methyl-2-pyrrolidone) can be used. Mw is a polystyrene equivalent value.

  The content rate of each structural unit which forms a polyorganosiloxane compound (AP) is not specifically limited, It selects from the following range so that the sum total of each structural unit may be 100 mol%. Therefore, when the polyorganosiloxane compound (AP) is represented by the general formula (I), when there is a structural unit other than the structural unit A and the structural unit B, the content of both the structural unit A and the structural unit B is The total does not have to be 100 mol%.

When the polyorganosiloxane compound (AP) is represented by the general formula (I), the structural unit A represented by-(Si (R ¹ ) (R ² ) -O)-in the polyorganosiloxane compound (AP) Is preferably 1 to 99 mol%, more preferably 1 to 90 mol%, and particularly preferably 1 to 40 mol%.
Moreover, it is preferable that the content rate b of the structural unit B represented by-(Si (R ^{< 3} >) (L ^{< 1} > ^-Rx ))-is 1-99 mol%, and is 1-90 mol%. Is more preferable, and it is especially preferable that it is 1-60 mol%.

When the polyorganosiloxane compound (AP) is represented by the general formula (Ia), the content a of the structural unit A is preferably 1 to 98 mol%, and preferably 1 to 60 mol%. More preferably, it is 1-40 mol% especially preferable.
The content rate b of the structural unit B is preferably 1 to 98 mol%, more preferably 1 to 90 mol%, and particularly preferably 1 to 60 mol%.
In the polyorganosiloxane compound (AP), the content d of the structural unit D represented by — (Si (R ⁵ ) (H)) — is preferably 1 to 90 mol%, and preferably 1 to 60 mol%. It is more preferable that it is 1 to 40 mol%.

When the polyorganosiloxane compound (AP) is represented by the general formula (II), the content a of the structural unit A is preferably 1 to 98 mol%, more preferably 1 to 90 mol%. 1 to 40 mol% is particularly preferable.
Further, the content b of the structural unit B is preferably 1 to 98 mol%, more preferably 1 to 90 mol%, and particularly preferably 1 to 60 mol%.
Polyorganosiloxane compound ^{(AP), - (Si (} R 4) (L 2 -R y)) - content c of the structural unit C represented by is preferably 1-98 mol%, 1 More preferably, it is -90 mol%, It is further more preferable that it is 1-60 mol%, It is especially preferable that it is 1-40 mol%.

When the polyorganosiloxane compound (AP) is represented by the general formula (II-a), the content a of the structural unit A is preferably 1 to 97 mol%, and preferably 1 to 90 mol%. More preferably, it is 1-40 mol% especially preferable.
The content b of the structural unit B is preferably 1 to 97 mol%, more preferably 1 to 90 mol%, and particularly preferably 1 to 60 mol%.
The content c of the structural unit C is preferably 1 to 97 mol%, more preferably 1 to 90 mol%, and particularly preferably 1 to 60 mol%.
The content d of the structural unit D is preferably 1 to 97 mol%, more preferably 1 to 90 mol%, and particularly preferably 1 to 40 mol%.

  Moreover, it is preferable that the content rate in the polyorganosiloxane compound of the said structural unit E is 1-40 mol%, It is more preferable that it is 1-20 mol%, It is that it is 1-10 mol%. Particularly preferred.

The content of each structural unit can be determined, for example, by ¹ H-NMR or ¹³ C-NMR using an NMR measuring apparatus (Bruker Biospin Corporation; AVANCEIII400 type).

  Specific examples of the polyorganosiloxane compound (AP) used in the present invention are shown below, but the present invention is not limited thereto. In addition, in the following concrete, the content rate of each structural unit exists in the said range.

The polyorganosiloxane compound (AP) is converted into a conventionally known method such as hydrolysis, condensation reaction, addition reaction, or ring-opening polymerization using a precursor that becomes a repeating unit constituting each structural unit, such as silicon alkoxide. It can be synthesized accordingly.
Further, as described above,-(L ¹ -R ^x ),-(L ² -R ^y ) and the like can also be synthesized by hydrosilylation reaction.
Although it does not specifically limit as polyorganosiloxane which has a hydrosilyl group which can be used for this hydrosilylation reaction, The following are mentioned.
Examples of the polyhydrosiloxane include HMS-991, HMS992, and HMS-993 (trade names, all manufactured by Gelest Co.), and copolymers of hydrosiloxane and dimethylsiloxane include, for example, HMS-013, 031, 064, 071, 082, 151, 301, 501 (trade names, all manufactured by Gelest), as a copolymer of methylhydrosiloxane and phenylmethylsiloxane, for example, HPM-502 (trade name, manufactured by Gelest) Can be mentioned.

  The content of the polyorganosiloxane compound (AP) in the curable composition is preferably 30 to 100% by mass, more preferably 40 to 90% by mass, and particularly preferably the total solid content of the curable composition. It is 45-90 mass%.

[Compound (B) having radical or cationic polymerizable functional group]
The curable composition of the present invention preferably contains a compound having a radical or cationic polymerizable functional group (simply referred to as compound (B)) from the viewpoint of curability.
From the viewpoint of curability, the radical polymerizable functional group and the cationic polymerizable functional group are preferably two or more, and more preferably three or more.

<Compound (B1) having a radical polymerizable functional group>
The compound (B1) is preferably a compound having an ethylenically unsaturated group as a radical polymerizable functional group capable of radical polymerization, and is not particularly limited as long as it is a compound having at least one radical polymerizable functional group in the molecule. . The compound (B1) preferably has two or more radically polymerizable functional groups in the molecule, more preferably 2 to 6. Compound (B1) may be used alone or in combination of two or more.

  Examples of the compound (B1) include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and salts thereof, anhydrides having an ethylenically unsaturated group, acrylonitrile, styrene. , Unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated urethane, and the like.

  Specific examples of acrylic acid compounds include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, and bis (4-acryloxypolyethoxyphenyl). Propane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol Triacrylate, pentaerythritol tetraa Relate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N- methylol acrylamide, diacetone acrylamide, epoxy acrylate.

  Specific examples of the methacrylic acid compound include methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, and ethylene. Examples include glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and the like. It is done.

Other examples include allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate.
In addition, "Crosslinking agent handbook" (Yamashita Shinzo, 1981 Taiseisha), "UV / EB curing handbook (raw material)" (Kato Kiyosumi, 1985, Kobunshi Publishing), "UV / EB curing technology" Commercially available products or publicly known radical polymerization described in “Application and Market of Radtech” (79 pp. 1989, CMC), “Polyester Resin Handbook” (Eiichiro Takiyama, 1988, Nikkan Kogyo Shimbun) Or crosslinkable monomers, oligomers and polymers can be used.

  As the compound (B1), for example, described in JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, JP-A-9-134011 and the like. The photocurable polymerizable compound material used for the photopolymerizable composition used can also be mentioned.

  The content of the compound (B1) in the curable composition is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% with respect to the total solid content of the curable composition. % By mass.

<Compound having cationic polymerizable functional group (B2)>
The compound (B2) is preferably a compound having any one of an epoxy group, an oxetanyl group and a vinyl ether group as a cationically polymerizable functional group capable of cationic polymerization, and a compound having at least one cationically polymerizable functional group in the molecule If it is, it will not specifically limit. The compound (B2) preferably has two or more cationically polymerizable functional groups in the molecule, and more preferably has 2 to 6 functional groups. A compound (B2) can use 1 type (s) or 2 or more types together.

  Examples of the compound (B2) include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and Examples thereof include epoxy compounds, vinyl ether compounds, and oxetane compounds described in JP-A No. 2001-220526.

Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts with epichlorohydrin. Specifically, for example, di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl ether of hydrogenated bisphenol A or its alkylene oxide adduct, and novolak type epoxy resin can be used. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably. Specifically, the said epoxy group and oxetanyl group condensed with rings, such as an alicyclic ring, are mentioned.

  Examples of the aliphatic epoxide include an aliphatic polyhydric alcohol or a di- or polyglycidyl ether of an alkylene oxide adduct thereof. Typical examples include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or diglycidyl ether of 1,6-hexanediol, diglycidyl ether of alkylene glycol, glycerin or its alkylene oxide adduct di- or tri- Polyglycidyl ethers of polyhydric alcohols such as glycidyl ether, diglycidyl ethers of polyethylene glycol or alkylene oxide adducts thereof, diglycidyl ethers of polyalkylene glycols typified by diglycidyl ethers of polypropylene glycol or alkylene oxide adducts thereof, etc. Can be mentioned. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

In the present invention, a monofunctional epoxy compound and a polyfunctional epoxy compound can be used.
Examples of monofunctional epoxy compounds include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene. Monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. Is mentioned.

  Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S di Glycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) Rumethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-di Examples thereof include epoxy octane, 1,2,5,6-diepoxycyclooctane and the like.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

Examples of vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds.
Specific examples of the monofunctional vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, cyclohexane dimethanol monovinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, Ethoxy ethyl Vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl Vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxy polyethylene glycol vinyl ether, isopropenyl ether-o-propylene carbonate Over doors and the like.

Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butylene glycol divinyl ether, and butanediol. Divinyl ethers such as divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, and the like; trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane Travinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether , Propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, propylene oxide Polyfunctional vinyl ethers such as pressurized dipentaerythritol hexa vinyl ether.
As the vinyl ether compound, a di- or trivinyl ether compound is preferable in terms of curability and the like, and a divinyl ether compound is particularly preferable.

  The oxetane compound may be any compound having an oxetane ring. For example, oxetane compounds described in JP 2001-220526 A, JP 2001-310937 A, and JP 2003-341217 A may be used. .

Moreover, as a compound which has 1-4 oxetane rings in a molecule | numerator, it shows by General formula (1)-(4) described in Paragraph [0037]-Paragraph [0051] of Unexamined-Japanese-Patent No. 2007-91946. Also included are compounds.
The oxetane compound is preferably a compound having 1 to 4 oxetane rings in its structure.

  The content of the compound (B2) in the curable composition is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% with respect to the total solid content of the curable composition. % By mass.

[Polymerization initiator]
The curable composition of the present invention preferably contains a polymerization initiator. As the polymerization initiator, a radical polymerization initiator or a cationic polymerization initiator is used depending on R ^y and the compound (B).

<Radical polymerization initiator>
As a radical polymerization initiator, a well-known thing can be used without being specifically limited. Preferably, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds , Compounds having a carbon halogen bond, alkylamine compounds, and the like.
The radical polymerization initiator may be used alone or in combination. From the viewpoint of curing, it is preferable to use two or more radical polymerization initiators in combination.
The content of the radical polymerization initiator in the curable composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, in terms of the total solid content of the curable composition. More preferably, it is 0.1-7 mass%.

<Cationic polymerization initiator>
As a cationic polymerization initiator, a well-known thing can be used without being specifically limited. Examples of the sulfonium compound include CP-100P (trade name, manufactured by San Apro), and examples of the iodonium compound include WPI-113 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.).
Further, “a compound that generates an acid upon irradiation with radiation and an onium salt halide that decomposes upon irradiation with radiation” described in JP-A-2007-91946 can also be used.
Cationic polymerization initiators may be used alone or in combination.

  The content of the cationic polymerization initiator in the curable composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass, in terms of the total solid content of the curable composition. More preferably, it is 0.1-5 mass%.

[Other ingredients]
The curable composition of the present invention may contain various additives in addition to the above components. Examples thereof include a solvent, a resin as a binder, an antioxidant, an ultraviolet absorber, a surfactant, a viscosity modifier, a gelling agent, an inorganic or organic filler, and the like.

Examples of the solvent include, but are not limited to, ethylene glycol monomethyl ether, methyl cellosolve acetate, diethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, butyl acetate, ethyl lactate, butyl lactate, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol and the like can be used. These organic solvents can be used alone or in combination of two or more.
Of these, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, ethanol, and 1-butanol are preferable from the viewpoint of improving leveling properties.

[Preparation method]
The curable composition of this invention can be prepared by mixing the said component. The conditions at this time are not particularly limited. For example, it can be prepared by mixing by stirrer stirring, ultrasonic dispersion, ball mill dispersion or the like.

[Usage]
The curable composition of the present invention is a material for forming an insulating layer of a semiconductor element, preferably a gate insulating layer of a TFT, particularly preferably an insulating layer provided between an electrode and a semiconductor layer provided on the electrode. Used.

[Insulating film]
The insulating film of the present invention is a film formed by curing the curable composition of the present invention.
When the curable composition of the present invention is cured, for example, the radical or cation polymerizable functional group of the structural unit C of the polyorganosiloxane compound (AP) and the compound (B) undergoes a polymerization (curing) reaction to form a polyorganosiloxane. A cured product obtained by crosslinking the compound (AP) in a network form. At this time, the heterocyclic group R ^x is not subjected to the polymerization reaction and remains in a free (unreacted) state even after the curable composition is cured. Thereby, the applicability | paintability of organic-semiconductor material can be improved and stability of a TFT characteristic can be improved.

When the curable composition of the present invention is thermally cured, the curing conditions are not particularly limited as long as the curing reaction proceeds. For example, the heating temperature is preferably 20 to 230 ° C, more preferably 40 to 200 ° C, and the heating time. Is preferably 5 minutes to 24 hours, more preferably 10 minutes to 12 hours.
In the case of photocuring the curable composition of the present invention, the curing conditions are not particularly limited as long as the curing reaction proceeds. Is mentioned.
The radiation to be irradiated is not particularly limited as long as it can impart energy capable of generating an initiation species from the polymerization initiator, and examples thereof include α rays, γ rays, X rays, ultraviolet rays, visible rays, and electron beams.

[Thin film transistor]
If the thin-film transistor of this invention has an insulating film formed by hardening | curing the curable composition of this invention as a gate insulating layer, another structure will not be specifically limited.
As the thin film transistor of the present invention, an organic thin film transistor (OTFT) including an organic semiconductor layer made of an organic semiconductor material is particularly preferable.

  The preferred TFT of the present invention will be described below, but the TFT of the present invention is not limited to this.

  The TFT of the present invention is provided on a substrate, in contact with the gate electrode, the semiconductor layer, the gate insulating layer provided between the gate electrode and the semiconductor layer, and the semiconductor layer, and is connected through the semiconductor layer. A source electrode and a drain electrode; In a TFT, a semiconductor layer and a gate insulating layer are usually provided adjacent to each other. In such a TFT, the current flowing between the source electrode and the drain electrode is controlled as described above.

  A preferred structure of the TFT of the present invention will be described with reference to the drawings. The TFT shown in each drawing is a schematic diagram for facilitating the understanding of the present invention, and the size or relative size relationship of each member may be changed for convenience of explanation. Is not shown as it is. Moreover, it is not limited to the external shape and shape shown by these drawings except the matter prescribed | regulated by this invention. For example, in FIGS. 1A and 1B, the gate electrode 5 does not necessarily cover all of the substrate 6, and a form provided in the central portion of the substrate 6 is also preferable as a form of the TFT of the present invention. .

1A to 1D are longitudinal sectional views each schematically showing a typical preferable structure of a TFT. 1A to 1D, 1 is a semiconductor layer, 2 is a gate insulating layer, 3 is a source electrode, 4 is a drain electrode, 5 is a gate electrode, and 6 is a substrate.
1A is a bottom gate / bottom contact structure, FIG. 1B is a bottom gate / top contact structure, FIG. 1C is a top gate / bottom contact structure, and FIG. 1D is a top. A TFT having a gate-top contact structure is shown.
All of the above four forms are included in the TFT of the present invention. Although not shown, an overcoat layer may be formed on the top of each TFT in the drawing (the top on the side opposite to the substrate 6).

In the bottom gate structure, the gate insulating layer 2 is provided between the gate electrode 5 and the semiconductor layer 1 on the gate electrode 5. Specifically, the gate electrode 5, the gate insulating layer 2, The semiconductor layers 1 are arranged in this order. On the other hand, in the top gate structure, a semiconductor layer 1, a gate insulating layer 2, and a gate electrode 5 are arranged in this order on a substrate 6.
In the bottom contact structure, the source electrode 3 and the drain electrode 4 are arranged on the substrate 6 side (that is, the lower side in FIG. 1) with respect to the semiconductor layer 1. On the other hand, in the top contact structure, the source electrode 3 and the drain electrode 4 are arranged on the opposite side of the substrate 6 with respect to the semiconductor layer 1.

[substrate]
The substrate may be any substrate that can support the TFT and the display panel or the like produced thereon. The substrate is not particularly limited as long as the surface is insulative, has a sheet shape, and has a flat surface.

An inorganic material may be used as the material for the substrate. Examples of substrates made of inorganic materials include various glass substrates such as soda lime glass and quartz glass, various glass substrates having an insulating film formed on the surface, silicon substrates having an insulating film formed on the surface, sapphire substrates, and stainless steel. , Metal substrates made of various alloys such as aluminum and nickel, various metals, metal foil, paper, and the like.
When the substrate is made of a conductive or semiconducting material such as stainless steel sheet, aluminum foil, copper foil or silicon wafer, an insulating polymer material or metal oxide is usually applied or laminated on the surface. Used.

Further, an organic material may be used as the material of the substrate. For example, polymethyl methacrylate (polymethyl methacrylate, PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyethersulfone (PES), polyimide, polyamide, polyacetal, polycarbonate (PC), polyethylene terephthalate (PET), Examples thereof include a flexible plastic substrate (also referred to as a plastic film or a plastic sheet) made of an organic polymer exemplified by polyethylene naphthalate (PEN), polyethyl ether ketone, polyolefin, and polycycloolefin. Moreover, the thing formed with the mica can also be mentioned.
If such a flexible plastic substrate or the like is used, for example, a TFT can be incorporated or integrated into a display device or electronic device having a curved shape.

Since the organic material forming the substrate is difficult to be softened when other layers are laminated or heated, the glass transition point is preferably high and the glass transition point is preferably 40 ° C. or higher. In addition, it is preferable that the coefficient of linear expansion is small from the viewpoint that the dimensional change is hardly caused by the heat treatment at the time of manufacture and the transistor performance is stable. For example, a material having a linear expansion coefficient of 25 × 10 ⁻⁵ cm / cm · ° C. or less is preferable, and a material having a coefficient of 10 × 10 ⁻⁵ cm / cm · ° C. or less is more preferable.
In addition, the organic material constituting the substrate is preferably a material having resistance to a solvent used at the time of TFT fabrication, and a material excellent in adhesion to the gate insulating layer and the electrode is preferable.
Furthermore, it is also preferable to use a plastic substrate made of an organic polymer having a high gas barrier property.
It is also preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate, or to deposit or laminate an inorganic material.

  In addition to the above, a conductive substrate (a substrate made of metal such as gold or aluminum, a substrate made of highly oriented graphite, a stainless steel substrate, etc.) can also be used as the substrate.

  On the substrate, a functional layer such as a buffer layer for improving adhesion and flatness, a barrier film for improving gas barrier properties, and a surface treatment layer such as an easy adhesion layer may be formed on the surface. Further, surface treatment such as corona treatment, plasma treatment, UV / ozone treatment may be performed.

  The thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less. On the other hand, it is preferably 0.01 mm or more, and more preferably 0.05 mm or more. In particular, in the case of a plastic substrate, the thickness is preferably about 0.05 to 0.1 mm. In the case of a substrate made of an inorganic material, the thickness is preferably about 0.1 to 10 mm.

[Gate electrode]
As the gate electrode, a conventionally known electrode used as a gate electrode of a TFT can be used. A conductive material (also referred to as an electrode material) constituting the gate electrode is not particularly limited. For example, metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, molybdenum, titanium, magnesium, calcium, barium, sodium, palladium, iron, manganese; InO ₂ , SnO ₂ , indium / tin oxide (ITO ), Fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO) and other conductive metal oxides; polyaniline, polypyrrole, polythiophene, polyacetylene, poly (3,4-ethylenedioxy) Conductive polymers such as thiophene) / polystyrene sulfonic acid (PEDOT / PSS); acids such as hydrochloric acid, sulfuric acid, sulfonic acid, Lewis acids such as PF ₆ , AsF ₅ , FeCl ₃ , halogen atoms such as iodine, sodium, potassium Conductivity with dopants such as metal atoms added Polymers, as well as carbon black, graphite powder, a composite material of the conductive dispersed metal fine particles and the like. These materials may be used alone or in combination of two or more in any combination and ratio.
Further, the gate electrode may be a single layer made of the above conductive material, or two or more layers may be stacked.

There is no limitation on the method of forming the gate electrode. For example, a film formed by physical vapor deposition (PVD) such as vacuum vapor deposition, chemical vapor deposition (CVD), sputtering, printing (coating), transfer, sol-gel, or plating is necessary. Accordingly, there is a method of patterning into a desired shape.
In the coating method, a solution, paste, or dispersion of the above material can be prepared and applied, and a film can be formed or an electrode can be directly formed by drying, baking, photocuring, aging, or the like.
In addition, inkjet printing, screen printing, (reversal) offset printing, letterpress printing, intaglio printing, lithographic printing, thermal transfer printing, microcontact printing, etc. allow for desired patterning, simplifying processes, reducing costs, and speeding up It is preferable in terms of conversion.
Even when a spin coating method, a die coating method, a micro gravure coating method, or a dip coating method is adopted, patterning can be performed in combination with the following photolithography method or the like.

Examples of the photolithography method include a method in which a patterning of a photoresist is combined with etching such as wet etching with an etchant or dry etching with reactive plasma, a lift-off method, or the like.
As another patterning method, a method of irradiating the material with an energy beam such as a laser or an electron beam to polish the material or changing the conductivity of the material may be used.
Furthermore, the method of transferring the composition for gate electrodes printed on support bodies other than a board | substrate on base layers, such as a board | substrate, is also mentioned.

  Although the thickness of a gate electrode is arbitrary, 1 nm or more is preferable and 10 nm or more is especially preferable. Moreover, 500 nm or less is preferable and 200 nm or less is especially preferable.

[Gate insulation layer]
The gate insulating layer is not particularly limited as long as it is an insulating layer, and may be a single layer or a multilayer.
The gate insulating layer is formed of the insulating film of the present invention. The gate insulating film can be formed by applying and curing the curable composition of the present invention on the surface of the gate electrode 5 or the semiconductor layer 1 or the like.
The curable composition, curing method and conditions of the present invention are as described above.

The gate insulating layer is formed of a cured product in which the heterocyclic group R ^x exists in a free state. Thereby, the applicability | paintability of organic-semiconductor material can be improved and stability of a TFT characteristic can be improved. Although the details are not yet clear, it is thought as follows. In other words, the free heterocyclic group R ^x forms a domain in the hydrophobic insulating film, but when a relatively high-polarity organic solvent organic semiconductor material is applied on the insulating film, molecular free molecules are formed near the surface. It is considered that the polarity of the surface changes due to restructuring, and the coating film tends to be uniform. In addition, the free heterocyclic group R ^x strengthens the interaction with the electrode in contact with the insulating film, and improves the adhesion between the insulating film and the electrode. When the adhesion is improved, it is considered that the migration from the electrode is suppressed by suppressing the mixing of moisture from the interface and the like, and the generation of voids, and as a result, the wet heat stability of the TFT characteristics is improved.
Moreover, when the polyorganosiloxane compound (AP) has a structure represented by the general formula (II), the effect of improving the wet heat stability of the TFT characteristics is further enhanced. Although the details are not yet clear, it is considered that the introduction of a hydrophobic cross-linked structure suppresses the penetration of moisture into the semiconductor, and also improves the heat resistance during heat treatment such as annealing. .

The gate insulating layer may be subjected to surface treatment such as corona treatment, plasma treatment, UV / ozone treatment, etc. In this case, it is preferable that the surface roughness due to the treatment is not roughened. Preferably, the arithmetic mean roughness of the surface of the gate insulating layer Ra or root mean square roughness _{R MS} is 0.5nm or less.

[Self-assembled monolayer (SAM)]
A self-assembled monolayer may be formed on the gate insulating layer.
The compound that forms the self-assembled monolayer is not particularly limited as long as it is a compound that self-assembles. For example, one or more compounds represented by the following formula 1S are used as the compound that self-assembles. be able to.
Formula 1S: R ^1S -X ^S

In Formula 1S, R ^1S represents any of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group (thienyl, pyrrolyl, pyridyl, fluorenyl, etc.).
X ^S represents an adsorptive or reactive substituent, specifically, —SiX ⁴ X ⁵ X ⁶ group (X ⁴ represents a halide group or an alkoxy group, and X ⁵ and X ⁶ are each independently a halide group. Represents an alkoxy group, an alkyl group, or an aryl group, and X ⁴ , X ⁵ , and X ⁶ are preferably the same, more preferably a chloro group, a methoxy group, and an ethoxy group, and a phosphonic acid group (- PO ₃ H ₂ ), phosphinic acid group (—PRO ₂ H, R is an alkyl group), phosphoric acid group, phosphorous acid group, amino group, halide group, carboxy group, sulfonic acid group, boric acid group (—B ( OH) ₂ ), a hydroxy group, a thiol group, an ethynyl group, a vinyl group, a nitro group, or a cyano group.

R ^1S is preferably not branched, for example, a linear normal alkyl (n-alkyl) group, a ter-phenyl group in which three phenyl groups are arranged in series, or a para-position of the phenyl group. A structure in which n-alkyl groups are arranged on both sides is preferable. The alkyl chain may have an ether bond, and may have a carbon-carbon double bond or a triple bond.

Self-assembled monolayer layer, adsorptive or reactive substituent X ^S is, interacting with the reactive sites (e.g., -OH groups) of the corresponding surface of the gate insulating layer, by forming the adsorption or reaction bonded Formed on the gate insulating layer. When the molecules are packed more densely, the surface of the self-assembled monolayer provides a smoother surface with a lower surface energy. Therefore, the main skeleton of the compound represented by the above formula 1S is linear. It is preferable that the molecular length is uniform.

  Specifically, as a particularly preferable example of the compound represented by Formula 1S, for example, alkyl such as methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, octadecyltrichlorosilane, and phenethyltrichlorosilane Alkyltrialkoxysilane compounds such as trichlorosilane compounds, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, alkylphosphonic acid, arylphosphonic acid, alkyl Examples thereof include carboxylic acid, arylphosphonic acid, alkylboric acid group, arylboric acid group, alkylthiol group, and arylthiol group.

The self-assembled monolayer may be formed using a method in which the above compound is deposited on the gate insulating layer under vacuum, a method in which the gate insulating layer is immersed in a solution of the above compound, a Langmuir-Blodgett method, or the like. it can. For example, it can form by processing a gate insulating layer with the solution which melt | dissolved the alkylchlorosilane compound or the alkyl alkoxysilane compound in the organic solvent 1-10 mass%. In the present invention, the method for forming the self-assembled monolayer is not limited to these.
For example, as a preferable method for obtaining a denser self-assembled monolayer, Langmuir 19, 1159 (2003) and J. Org. Phys. Chem. B 110, 21101 (2006) etc. are mentioned.

Specifically, the gate insulating layer is immersed in a highly volatile dehydrating solvent in which the above compound is dispersed to form a film, the gate insulating layer is taken out, and if necessary, the above compound such as annealing and the gate insulating layer After performing the above reaction step, the film can be washed with a dehydrated solvent and then dried to form a self-assembled monolayer.
Although it does not specifically limit as a dehydrating solvent, For example, chloroform, a trichloroethylene, anisole, diethyl ether, hexane, toluene etc. can be used individually or in mixture.
Furthermore, it is preferable to dry the film in a dry atmosphere or by spraying a dry gas. It is preferable to use an inert gas such as nitrogen as the dry gas. By using such a method for producing a self-assembled monolayer, a dense self-assembled monolayer without agglomeration or defects is formed. Can be suppressed to 0.3 nm or less.

[Semiconductor layer]
The semiconductor layer is a layer that exhibits semiconductor properties and can accumulate carriers.
The semiconductor layer is formed of an organic semiconductor compound (also simply referred to as an organic semiconductor).
The organic semiconductor demonstrated below may use 1 type, or may use 2 or more types together.

It does not specifically limit as an organic semiconductor, An organic polymer, its derivative (s), a low molecular weight compound, etc. are mentioned.
In the present invention, the low molecular compound means a compound other than the organic polymer and its derivative. That is, it refers to a compound having no repeating unit. As long as the low molecular weight compound is such a compound, the molecular weight is not particularly limited. The molecular weight of the low molecular weight compound is preferably 300 to 2000, and more preferably 400 to 1000.

  Examples of the low molecular weight compound include condensed polycyclic aromatic compounds. For example, naphthacene, pentacene (2,3,6,7-dibenzoanthracene), hexacene, heptacene, dibenzopentacene, tetrabenzopentacene and other acenes, anthradithiophene, pyrene, benzopyrene, dibenzopyrene, chrysene, perylene, coronene, terylene , Ovalene, quaterrylene, circumanthracene, and derivatives obtained by substituting a part of these carbon atoms with atoms such as N, S, O, etc., or at least one hydrogen atom bonded to the carbon atom is a functional group such as a carbonyl group Derivatives substituted with a group (perixanthenoxanthene and dioxaanthanthrene compounds including such derivatives, triphenodioxazine, triphenodithiazine, hexacene-6,15-quinone, etc.) and other functional groups of the above hydrogen atom Derivatives substituted with groups It is possible.

  Further, metal phthalocyanine represented by copper phthalocyanine, tetrathiapentalene and derivatives thereof, naphthalene-1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethylbenzyl) naphthalene— 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (1H, 1H-perfluorooctyl), N, N′-bis (1H, 1H-perfluorobutyl), N, N′-dioctylnaphthalene -1,4,5,8-tetracarboxylic acid diimide derivatives, naphthalene tetracarboxylic acid diimides such as naphthalene-2,3,6,7-tetracarboxylic acid diimide, anthracene-2,3,6,7-tetracarboxylic acid Condensed ring tetracarboxylic acid diimide such as anthracene tetracarboxylic acid diimide such as diimide, C60, C70, 76, C78, C84 fullerene and derivatives thereof such as, for SWNT such as carbon nanotubes, merocyanine dyes, may be mentioned such dyes and their derivatives, such as hemicyanine dyes.

  Furthermore, polyanthracene, triphenylene, quinacridone can be mentioned.

  Examples of the low molecular weight compound include 4,4′-biphenyldithiol (BPDT), 4,4′-diisocyanobiphenyl, 4,4′-diisocyano-p-terphenyl, 2,5-bis (5 '-Thioacetyl-2'-thiophenyl) thiophene, 2,5-bis (5'-thioacetoxyl-2'-thiophenyl) thiophene, 4,4'-diisocyanophenyl, benzidine (biphenyl-4,4'- Diamine), TCNQ (tetracyanoquinodimethane), tetrathiafulvalene (TTF) and its derivatives, tetrathiafulvalene (TTF) -TCNQ complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex , A charge transfer complex represented by TCNQ-iodine complex, biphenyl-4,4′-dica Boronic acid, 1,4-di (4-thiophenylacetylinyl) -2-ethylbenzene, 1,4-di (4-isocyanophenylacetylinyl) -2-ethylbenzene, 1,4-di (4- Thiophenylethynyl) -2-ethylbenzene, 2,2 ″ -dihydroxy-1,1 ′: 4 ′, 1 ″ -terphenyl, 4,4′-biphenyldiethanal, 4,4′-biphenyldiol, 4, 4′-biphenyl diisocyanate, 1,4-diacetinylbenzene, diethylbiphenyl-4,4′-dicarboxylate, benzo [1,2-c; 3,4-c ′; 5,6-c ″] tris [1,2] dithiol-1,4,7-trithione, α-sexithiophene, tetrathiatetracene, tetraselenotetracene, tetratellurtetracene, poly (3-alkylthiophene) Poly (3-thiophene-β-ethanesulfonic acid), poly (N-alkylpyrrole) poly (3-alkylpyrrole), poly (3,4-dialkylpyrrole), poly (2,2′-thienylpyrrole), Poly (dibenzothiophene sulfide) can be exemplified.

  The organic semiconductor is preferably a low molecular compound, and among them, a condensed polycyclic aromatic compound is preferable. The condensed polycyclic aromatic compound has a high effect of improving carrier mobility and durability, and also exhibits an excellent threshold voltage reduction effect.

  The condensed polycyclic aromatic compound is preferably an acene represented by any one of the general formulas (A1) to (A4) and a compound represented by any one of the following general formulas (C) to (T). A compound represented by any one of the following general formulas (C) to (T) is more preferable because it is likely to be unevenly distributed with (C).

  Preferred acenes as the condensed polycyclic aromatic compound are those represented by the following general formula (A1) or (A2).

In the formula, R ^{A1 to} R ^A6 , X ^A1 and X ^A2 represent a hydrogen atom or a substituent.
Z ^A1 and Z ^A2 represent S, O, Se, or Te.
nA1 and nA2 represent an integer of 0 to 3. However, nA1 and nA2 are not 0 at the same time.

The substituents represented by R ^{A1 to} R ^A6 , X ^A1 and X ^A2 are not particularly limited, but are alkyl groups (for example, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, tert-pentyl, hexyl). Octyl, tert-octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.), a cycloalkyl group (eg, cyclopentyl, cyclohexyl etc.), an alkenyl group (eg, vinyl, allyl, 1-propenyl, 2-butenyl, 1,3- Butadienyl, 2-pentenyl, isopropenyl, etc.), alkynyl group (eg, ethynyl, propargyl, etc.), aromatic hydrocarbon group (aromatic carbocyclic group, aryl group, etc., for example, phenyl, p-chlorophenyl, mesityl, Tolyl, xylyl, naphthyl, antri , Azulenyl, acenaphthenyl, fluorenyl, phenanthryl, indenyl, pyrenyl, biphenylyl, etc.), aromatic heterocyclic groups (also called heteroaryl groups, such as pyridyl, pyrimidinyl, furyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrazolyl Group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, Isoxazolyl, isothiazolyl, furazanyl, thienyl, quinolyl, benzofuryl, dibenzofuryl, benzothienyl, dibenzothienyl, indolyl, carbazolyl, carbolinyl, diazacarbazolyl (carbolinyl carboline) Or a quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group, etc.), a heterocyclic group (heteroaryl ring group, etc.), for example, pyrrolidyl Group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy group (eg, cyclopentyloxy, cyclohexyloxy) Etc.), aryloxy groups (eg phenoxy, naphthyloxy etc.), alkylthio groups (eg methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio etc.), cycloalkylthio groups (Eg, cyclopentylthio, cyclohexylthio, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl, ethyloxycarbonyl, butyloxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), Aryloxycarbonyl groups (eg, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl groups (eg, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecyl) Aminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfo ), Acyl groups (eg, acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy groups (eg, Acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), amide groups (eg, methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, Cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, Silcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl groups (eg, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylamino) Carbonyl, dodecylaminocarbonyl, phenylaminocarbonyl, naphthylaminocarbonyl, 2-pyridylaminocarbonyl, etc.), ureido group (eg, methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.), sulfinyl groups (for example, methylsulfini , Ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfonyl groups (for example, methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, etc.), arylsulfonyl groups (phenylsulfonyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino groups (eg, amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino) , Dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.), halogen atoms (for example, fluorine Child, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl, trifluoromethyl, pentafluoroethyl, pentafluorophenyl, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group ( for example, trimethylsilyl, triisopropylsilyl, triphenylsilyl, phenyl diethyl silyl, etc.), a group represented by the following general formula (SG1) (provided that, ^{X A} can be mentioned Ge or Sn) or the like.
These substituents may further have a plurality of substituents. Examples of the substituent which may be plurally mentioned include the substituents represented by R ^{A1 to} R ^A6 above.

  Among the above acenes, those represented by the following general formula (A3) or (A4) are more preferable.

In the formula, R ^A7 , R ^A8 , X ^A1 and X ^A2 represent a hydrogen atom or a substituent. R ^A7 , R ^A8 , X ^A1 and X ^A2 may be the same or different. The substituents represented by R ^A7 and R ^A8 are preferably those listed above as substituents that can be employed as R ^{A1 to} R ^{A6 in the} general formulas (A1) and (A2).
Z ^A1 and Z ^A2 represent S, O, Se, or Te.
nA1 and nA2 represent an integer of 0 to 3. However, nA1 and nA2 are not 0 simultaneously.

In the general formula (A3) or (A4), R ^A7 and R ^A8 are preferably those represented by the following general formula (SG1).

In formula, R ^<A9 > -R <^A11> represents a substituent. X ^A represents Si, Ge or Sn. The substituents represented by R ^{A9 to} R ^A11 are preferably those listed above as substituents that can be employed as R ^{A1 to} R ^{A6 in} the general formulas (A1) and (A2).

  Specific examples of the acene or acene derivative represented by the general formulas (A1) to (A4) are shown below, but are not limited thereto.

  As the condensed polycyclic aromatic compound, compounds represented by the following general formulas (C) to (T) are also preferable.

In general formula (C), A ^C1 and A ^C2 represent an oxygen atom, a sulfur atom or a selenium atom. Preferably both A ^C1 and A ^C2 represent an oxygen atom and a sulfur atom, more preferably a sulfur atom. R ^{C1 to} R ^C6 represent a hydrogen atom or a substituent. At least one of R ^{C1 to} R ^C6 is a substituent represented by the following general formula (W).
In general formula (D), X ^D1 and X ^D2 represent NR ^D9 , an oxygen atom or a sulfur atom. A ^D1 represents CR ^D7 or N atom, A ^D2 represents CR ^D8 or N atom, and R ^D9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group. R ^{D1 to} R ^D8 represent a hydrogen atom or a substituent, and at least one of R ^{D1 to} R ^D8 is a substituent represented by the following general formula (W).
In general formula (E), X ^E1 and X ^E2 represent an oxygen atom, a sulfur atom or NR ^E7 . A ^E1 and A ^E2 represent CR ^E8 or a nitrogen atom. R ^{E1 to} R ^E8 represent a hydrogen atom or a substituent. At least one of R ^{E1 to} R ^E8 is a substituent represented by the following general formula (W).

In general formula (F), ^XF1 and ^XF2 represent an oxygen atom, a sulfur atom, or a selenium atom. X ^F1 and X ^F2 preferably represent an oxygen atom or a sulfur atom, and more preferably represent a sulfur atom. R ^{F1 to} R ^F10 , R ^Fa and R ^Fb represent a hydrogen atom or a substituent. At least one of R ^{F1 to} R ^F10 , R ^Fa and R ^Fb is a substituent represented by the general formula (W). p and q represent the integer of 0-2.
In General Formula (G), X ^G1 and X ^G2 represent NR ^G9 , an oxygen atom, or a sulfur atom. A ^G1 represents CR ^G7 or an N atom. A ^G2 represents CR ^G8 or an N atom. R ^G9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group. R ^{G1 to} R ^G8 represent a hydrogen atom or a substituent. At least one of R ^{G1 to} R ^G8 is a substituent represented by the following general formula (W).

In General Formula (H), X ^{H1 to} X ^H4 represent NR ^H7 , an oxygen atom, or a sulfur atom. X ^{H1 to} X ^H4 preferably represent a sulfur atom. R ^H7 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group. R ^{H1 to} R ^H6 represent a hydrogen atom or a substituent. At least one of R ^{H1 to} R ^H6 is a substituent represented by the following general formula (W).

In general formula (J), X ^J1 and X ^J2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR ^J9 . X ^J3 and X ^J4 represent an oxygen atom, a sulfur atom or a selenium atom. X ^J1 , X ^J2 , X ^J3 and X ^J4 preferably represent a sulfur atom. R ^{J1 to} R ^J9 represent a hydrogen atom or a substituent. At least one of R ^{J1 to} R ^J9 is a substituent represented by the following general formula (W).
In general formula (K), X ^K1 and X ^K2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR ^K9 . X ^K3 and X ^K4 represent an oxygen atom, a sulfur atom or a selenium atom. X ^K1 , X ^K2 , X ^K3 and X ^K4 preferably represent a sulfur atom. R ^{K1 to} R ^K9 represent a hydrogen atom or a substituent. At least one of R ^{K1 to} R ^K9 is a substituent represented by the following general formula (W).
In the general formula (L), X ^L1 and X ^L2 represent an oxygen atom, a sulfur atom or NR ^L11 . X ^L1 and X ^L2 preferably represent an oxygen atom or a sulfur atom. R ^{L1 to} R ^L11 represent a hydrogen atom or a substituent, and at least one of R ^{L1 to} R ^L11 is a substituent represented by the following general formula (W).

In formula (M), X ^M1 and X ^M2 represent an oxygen atom, a sulfur atom, a selenium atom or NR ^M9 . X ^M1 and X ^M2 preferably represent a sulfur atom. R ^{M1 to} R ^M9 represent a hydrogen atom or a substituent. At least one of R ^{M1 to} R ^M9 is a substituent represented by the following general formula (W).
In general formula (N), ^XN1 and ^XN2 represent an oxygen atom, a sulfur atom, a selenium atom, or ^NRN13 . X ^N1 and X ^N2 preferably represent a sulfur atom. R ^{N1 to} R ^N13 represent a hydrogen atom or a substituent. At least one of R ^{N1 to} R ^N13 is a substituent represented by the following general formula (W).
In the general formula (P), X ^P1 and X ^P2 represent an oxygen atom, a sulfur atom, a selenium atom, or ^NRP13 . X ^P1 and X ^P2 preferably represent a sulfur atom. R ^{P1 to} R ^P13 represent a hydrogen atom or a substituent. At least one of R ^{P1 to} R ^P13 is a substituent represented by the following general formula (W).

In the general formula (Q), X ^Q1 and X ^Q2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR ^Q13 . X ^Q1 and X ^Q2 preferably represent a sulfur atom. R ^{Q1 to} R ^Q13 represent a hydrogen atom or a substituent. At least one of R ^{Q1 to} R ^Q13 is a substituent represented by the following general formula (W).
In the general formula (R), X ^R1 , X ^R2 and X ^R3 represent an oxygen atom, a sulfur atom, a selenium atom or NR ^R9 . X ^R1 , X ^R2 and X ^R3 preferably represent a sulfur atom. R ^{R1 to} R ^R9 represent a hydrogen atom or a substituent. At least one of R ^{R1 to} R ^R9 is a substituent represented by the following general formula (W).

In the general formula (S), X ^S1 , X ^S2 , X ^S3 and X ^S4 represent an oxygen atom, a sulfur atom, a selenium atom or NR ^S7 . X ^S1 , X ^S2 , X ^S3 and X ^S4 preferably represent a sulfur atom. R ^{S1 to} R ^S7 represent a hydrogen atom or a substituent. At least one of R ^{S1 to} R ^S7 is a substituent represented by the following general formula (W).
In the general formula (T), X ^T1 , X ^T2 , X ^T3 , and X ^T4 represent an oxygen atom, a sulfur atom, a selenium atom, or NR ^T7 . X ^T1 , X ^T2 , X ^T3 and X ^T4 preferably represent a sulfur atom. R ^{T1 to} R ^T7 represent a hydrogen atom or a substituent. At least one of R ^{T1 to} R ^T7 is a substituent represented by the following general formula (W).

In the following general formulas (C) to (T), R ^{C1 to} R ^C6 , R ^{D1 to} R ^D8 , R ^{E1 to} R ^E8 , R ^{F1 to} R ^F10 , R ^Fa and the like, each representing a hydrogen atom or a substituent. R ^Fb , R ^{G1 to} R ^G8 , R ^{H1 to} R ^H6 , R ^{J1 to} R ^J9 , R ^{K1 to} R ^K9 , R ^{L1 to} R ^L11 , R ^{M1 to} R ^M9 , R ^{N1 to} R ^N13 , R ^{P1 to} R ^P13 , R ^{Q1 to} R ^Q13 , R ^{R1 to} R ^R9 , R ^{S1 to} R ^S7, and R ^{T1 to} R ^T7 (hereinafter referred to as substituents R ^{C to} R ^T ) will be described.

The substituents R ^{C to} R ^T can be a halogen atom, an alkyl group (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl An alkyl group having 1 to 40 carbon atoms such as 2,6-dimethyloctyl, 2-decyltetradecyl, 2-hexyldecyl, 2-ethyloctyl, 2-decyltetradecyl, 2-butyldecyl, 1-octylnonyl , 2-ethyloctyl, 2-octyltetradecyl, 2-ethylhexyl, cycloalkyl, bicycloalkyl, tricycloalkyl, etc.), alkenyl groups (including 1-pentenyl, cycloalkenyl, bicycloalkenyl, etc.), alkynyl groups ( 1-pentynyl, trimethylsilyl Ethynyl, triethylsilylethynyl, tri-i-propylsilylethynyl, 2-p-propylphenylethynyl, etc.), aryl groups (phenyl, naphthyl, p-pentylphenyl, 3,4-dipentylphenyl, p-heptoxyphenyl) , 3,4-diheptoxyphenyl aryl groups having 6 to 20 carbon atoms, etc.), heterocyclic groups (may be referred to as heterocyclic groups, including 2-hexylfuranyl etc.), cyano groups, hydroxy groups Group, nitro group, acyl group (including hexanoyl, benzoyl, etc.), alkoxy group (including butoxy, etc.), aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (anilino group) ), Acylamino group, aminocarbonylamino group (including ureido group), alkoxy and Aryloxycarbonylamino group, alkyl and arylsulfonylamino group, mercapto group, alkyl and arylthio group (including methylthio, octylthio, etc.), heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl Groups, alkyl and aryloxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, phosphono groups, silyl groups (ditrimethylsiloxymethyl Butoxy group, etc.), hydrazino group, ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other known substituents Can be mentioned.

  These substituents may further have the above substituents.

Among these, as substituents that the substituents R ^{C to} R ^T can take, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, and a general formula (W) described later are represented. A group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, A heterocyclic group having 5 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and a group represented by the following general formula (W) are more preferable, and a group represented by the following general formula (W) is particularly preferable. A group represented by the following general formula (W) is more particularly preferable.

The alkyl group, alkenyl group, alkynyl group, acyl group, and aryl group of R ^D9 , R ^G9, and R ^H7 are each an alkyl group or an alkenyl group described in the substituents that the substituents R ^{C to} R ^T can take. , An alkynyl group, an acyl group, and an aryl group.
Moreover, a heteroaryl group is synonymous with the heteroaryl group ^{demonstrated by} the substituent of R ^{< A1} > -R < ^A6 >.

Formula ^{(W): - L-R} W for the group represented by is described.

In general formula (W), L is a divalent linking group represented by any one of the following general formulas (L-1) to (L-25) or two or more of the following general formulas (L-1) to (L -25) represents a divalent linking group to which the divalent linking group represented by any one is bonded. R ^W is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, a siloxane group, the number of silicon atoms is more than one It represents an oligosiloxane group or a substituted or unsubstituted trialkylsilyl group.

In the general formulas (L-1) to (L-25), the wavy line represents the bonding position with any ring forming each skeleton represented by the general formulas (C) to (T). In the present specification, when L represents a divalent linking group in which two or more divalent linking groups represented by any of the general formulas (L-1) to (L-25) are bonded, wavy lines The moiety is a divalent group represented by the bonding position with any ring forming each skeleton represented by the general formulas (C) to (T) and the general formulas (L-1) to (L-25). You may represent the coupling | bonding position with either of a coupling group.
* Represents a bonding position with Rw or a bonding position with a wavy line part of the general formulas (L-1) to (L-25).
M in the general formula (L-13) represents 4, m in the general formulas (L-14) and (L-15) represents 3, and m in the general formulas (L-16) to (L-20) represents 2 and m in (L-22) represents 6.
R 'in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-19) and (L-21) to (L-24) is independently It represents a hydrogen atom or a substituent, formula (L-1) and (L-2) in R 'may form a condensed ring by combining with R ^W adjacent to L, respectively.
R ^N represents a hydrogen atom or a substituent, and R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.

  Among these, the divalent linking groups represented by the general formulas (L-17) to (L-21), (L-23) and (L-24) are represented by the following general formulas (L-17A) to (L It is more preferably a divalent linking group represented by -21A), (L-23A) and (L-24A).

Here, a substituted or unsubstituted alkyl group, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted group. If a trialkylsilyl group substitutions present on the end of the substituent of the general formula (W) -R ^W alone and can also be interpreted in, be interpreted as -L-R ^W in the general formula (W) it can.
In the present invention, when a substituted or unsubstituted alkyl group having N carbon atoms in the main chain is present at the terminal of the substituent, the general formula (W an be interpreted as ^{-L-R W} in), it is not interpreted as -R ^W alone in the general formula (W). Specifically, "corresponds to L in the general formula (W) (L-1) 1 piece" and "Formula backbone corresponding to R ^W in (W) is the number of N-1 carbon substituted or unsubstituted It is interpreted as a substituent bonded to an “alkyl group of”. For example, when an n-octyl group, which is an alkyl group having 8 carbon atoms, is present at the terminal of the substituent, two R ′ are hydrogen atoms (L-1), and n-heptyl having 7 carbon atoms. Interpreted as a substituent bonded to a group. In addition, when the substituent represented by the general formula (W) is an alkoxy group having 8 carbon atoms, one linking group represented by the general formula (L-4) which is —O— and two R It is interpreted as a substituent in which one linking group represented by (L-1) where 'is a hydrogen atom and an n-heptyl group having 7 carbon atoms are bonded.
On the other hand, in the present invention, an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group. If a group is present at the end of the substituents on including a linking group as possible from the end of the substituent, it is interpreted as R ^W alone in the general formula (W). For example, when a — (OCH ₂ CH ₂ ) — (OCH ₂ CH ₂ ) — (OCH ₂ CH ₂ ) —OCH ₃ group is present at the end of the substituent, an oligooxyethylene having a repeating number v of oxyethylene units of 3 Interpreted as a single group substituent.

  When L forms a linking group to which a divalent linking group represented by any one of formulas (L-1) to (L-25) is bonded, formulas (L-1) to (L-25) The number of bonds of the divalent linking group represented by any of the above is preferably 2-4, more preferably 2 or 3.

As the substituent R ′ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24), those represented by the general formulas (C) to (T) What was illustrated as a substituent which substituent ^{RC- RT} can take can be mentioned. Among them, the substituent R ′ in the general formula (L-6) is preferably an alkyl group. When R ′ in (L-6) is an alkyl group, the alkyl group has 1 to 9 carbon atoms. It is preferable that it is 4-9, and it is more preferable from a viewpoint of chemical stability and carrier transportability, and it is further more preferable that it is 5-9. When R ′ in (L-6) is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of increasing carrier mobility.
The R ^N, may be mentioned those exemplified as the substituents which may take the substituents R ^C to R ^T. Among them a hydrogen atom or a methyl group is preferable as also R ^N.
R ^si is preferably an alkyl group. There are no particular limitations on the alkyl group R ^si can take, the preferred range of the alkyl group R ^si can take is the same as the preferred ranges of the alkyl group can take silyl group when R ^W is a silyl group. The alkenyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group preferably has 2 to 3 carbon atoms. . The alkynyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkynyl group, more preferably a branched alkynyl group, and the alkynyl group preferably has 2 to 3 carbon atoms. .

L is a divalent linking group represented by any one of the general formulas (L-1) to (L-5), (L-13), (L-17) or (L-18), or the general formula A divalent linkage in which two or more divalent linking groups represented by any one of (L-1) to (L-5), (L-13), (L-17) or (L-18) are bonded. A divalent linking group represented by any one of the general formulas (L-1), (L-3), (L-13) or (L-18) or the general formula (L- It is more preferable that the divalent linking group represented by 1), (L-3), (L-13) or (L-18) is a divalent linking group in which two or more are bonded. ), (L-3), (L-13) or (L-18), or a divalent linking group represented by formula (L-3), (L-13) or (L-18) Table in any one It is particularly preferred divalent divalent linking group represented by the linking group and formula (L-1) of that is a divalent linking group attached. A divalent linking group represented by any one of general formula (L-3), (L-13) or (L-18) and a divalent linking group represented by general formula (L-1) There divalent linking group bonded is preferably a divalent linking group represented by formula (L-1) binds to R ^W side.
From the viewpoints of chemical stability and carrier transportability, a divalent linking group including a divalent linking group represented by the general formula (L-1) is particularly preferable, and represented by the general formula (L-1). It is particularly preferable that L is a divalent linking group represented by the general formulas (L-18) and (L-1), and (L-1) bonded to R ^W, more particularly preferably more that R ^W is a substituted or unsubstituted alkyl group, a divalent linking group L is represented by the general formula (L-18A) and (L-1) Yes, (L-1) via bonded to R ^W, it is even more particularly preferred R ^W is a substituted or unsubstituted alkyl group.

In formula (W), R ^W may be a substituted or unsubstituted alkyl group. In formula (W), when L adjacent to R ^W is a divalent linking group represented by formula (L-1) is, R ^W represents a substituted or unsubstituted alkyl group, an oxyethylene group, It is preferably an oligooxyethylene group having 2 or more repeating oxyethylene units, a siloxane group, or an oligosiloxane group having 2 or more silicon atoms, more preferably a substituted or unsubstituted alkyl group.
In formula (W), when L adjacent to ^{R W} is a divalent linking group represented by formula (L-2) and (L-4) ~ (L -25) is, ^{R W} is It is more preferably a substituted or unsubstituted alkyl group.
In formula (W), when L adjacent to R ^W is a divalent linking group represented by the general formula (L-3) is, R ^W represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted The silyl group is preferable.

For R ^W is a substituted or unsubstituted alkyl group, it preferably has a carbon number of 4 to 17, chemical stability, more preferably from the viewpoint of carrier transport property that is 6 to 14, 6 to 12 More preferably it is. It R ^W are long-chain alkyl group having the above-mentioned range, and particularly a straight-chain alkyl group of chain increases the linearity of the molecule, from the viewpoint of capable of enhancing the carrier mobility.
If R ^W represents an alkyl group, a straight-chain alkyl group, even branched alkyl group, it may be a cyclic alkyl group, a straight-chain alkyl groups, increases the linearity of the molecules, to increase the carrier mobility It is preferable from the viewpoint that can be achieved.
Among these, the combination of R ^W and L in the general formula (W), a divalent linking group L in formula (C) ~ (T) is represented by formula (L-1), and, either ^{R W} is an alkyl group having a carbon number of 4 to 17 linear or, L is the general formula (L-3), any one Tsudehyo of (L-13) or (L-18) a divalent divalent divalent linking group linking group is attached, which is represented by the linking group and formula (L-1) that are, and that R ^W is a straight chain alkyl group, This is preferable from the viewpoint of increasing carrier mobility.

L is a divalent linking group represented by formula (L-1), and, if R ^W is an alkyl group having a carbon number of 4 to 17 linear, carbon atoms R ^W is a linear 6 It is more preferable that it is -14 alkyl group from a viewpoint of raising carrier mobility, and it is especially preferable that it is a linear C6-C12 alkyl group.

L is a divalent linking group represented by any one of general formulas (L-3), (L-13), or (L-18) and a divalent linking group represented by general formula (L-1). a divalent linking group of the linking group is bonded, and, if R ^W is a straight chain alkyl group, more preferably R ^W is an alkyl group having a carbon number of 4 to 17 linear, straight-chain The alkyl group having 6 to 14 carbon atoms is more preferable from the viewpoint of chemical stability and carrier transportability, and the straight chain alkyl group having 6 to 12 carbon atoms is particularly preferable from the viewpoint of increasing the carrier mobility. preferable.
On the other hand, from the viewpoint of enhancing the solubility in organic solvents, it is preferred that R ^W is a branched alkyl group.

The substituent when R ^W is an alkyl group having a substituent include a halogen atom, a fluorine atom is preferred. It is also possible if R ^W is an alkyl group having a fluorine atom is substituted for all the hydrogen atoms of the alkyl group fluorine atom to form a perfluoroalkyl group. However, it is preferred that R ^W is an unsubstituted alkyl group.

If R ^W is ethylene group or an oligo ethylene group, and represented by ^{R W} "oligooxyethylene group" _{herein, - (OCH 2 CH 2)} v refers to the group represented by OY ( The repeating number v of the oxyethylene unit represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent. In addition, when Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group. The repeating number v of oxyethylene units is preferably 2 to 4, and more preferably 2 to 3. The terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent. In this case, the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is particularly preferable.

R ^W is, for siloxane group or an oligosiloxane groups, the number of repetitions of the siloxane units is preferably from 2 to 4, more preferably 2 to 3. Further, it is preferable that a hydrogen atom or an alkyl group is bonded to the Si atom. When the alkyl group is bonded to the Si atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded thereto. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.

If L adjacent to R ^W is a divalent linking group represented by the general formula (L-3), it is also preferred R ^W is a substituted or unsubstituted silyl group. If R ^W is a substituted or unsubstituted silyl group Among them, it is preferred that R ^W is a substituted silyl group. Although there is no restriction | limiting in particular as a substituent of a silyl group, A substituted or unsubstituted alkyl group is preferable and it is more preferable that it is a branched alkyl group. If R ^W is a trialkylsilyl group, the carbon number of the alkyl group bonded to the Si atom is preferably from 1 to 3, for example, it is preferable to bind a methyl group or an ethyl group or an isopropyl group. The same alkyl group may be bonded to the Si atom, or different alkyl groups may be bonded thereto. The substituent when R ^W is a trialkylsilyl group having a substituent on the alkyl group is not particularly limited.

In formula (W), it is preferred that the total number of carbon atoms contained in L and ^{R W} is 5 to 18. If the total number of carbon atoms contained in L and R ^W is at least the lower limit within the above range, the carrier mobility is high, lower the driving voltage. If the total number of carbon atoms contained in L and R ^W is not more than the upper limit of the above range, solubility in an organic solvent is increased.
Preferably the total number of carbon atoms contained in L and ^{R W} is 5 to 14, more preferably 6 to 14, particularly preferably from 6 to 12, in particular more that 8 to 12 preferable.

In each compound represented by the general formulas (C) to (T), among the substituents R ^{C to} R ^T , the number of the groups represented by the general formula (W) is 1 to 4, and the carrier mobility is It is preferable from the viewpoint of increasing the solubility in an organic solvent, more preferably 1 or 2, and particularly preferably 2.

Among the substituents R ^{C to} R ^T , the position of the group represented by the general formula (W) is not particularly limited.
In the compound represented by the general formula (C), any one of R ^C1 , R ^C2 , R ^C3 and R ^C6 is preferably a group represented by the general formula (W), and R ^C1 and R ^C2 It is more preferable that both or both R ^C3 and R ^C6 are groups represented by the general formula (W).
In the compound represented by the general formula (D), R ^D6 is preferably a group represented by the general formula (W), and both R ^D5 and R ^D6 are represented by the general formula (W). More preferably, it is a group.
In the compound represented by the general formula (E), R ^E6 is preferably a group represented by the general formula (W), and both R ^E5 and R ^E6 are represented by the general formula (W). More preferably, it is a group. Further, when R ^E5 and R ^E6 are substituents other than the group represented by the general formula (W), it is also preferable that two R ^E7 are groups represented by the general formula (W).

In the compound represented by the general formula (F), it is preferable that at least one of R ^F2 , R ^F3 , R ^F8 and R ^F9 is a substituent represented by the general formula (W).
In the compound represented by the general formula (G), R ^G5 or R ^G6 is a group represented by the general formula (W) from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent. preferable.
In the compound represented by the general formula (H), R ^H4 or R ^H6 is preferably a group represented by the general formula (W), and R ^H4 or R ^H6 and R ^H3 or R ^H5 are generally used. The group represented by the formula (W) is more preferable.

In the compound represented by the general formula (J), R ^J8 is preferably a group represented by the general formula (W), and both R ^J8 and R ^J4 are represented by the general formula (W). More preferably, it is a group.
In the compound represented by the general formula (K), R ^K7 is preferably a group represented by the general formula (W), and both R ^K7 and R ^K3 are represented by the general formula (W). More preferably, it is a group.
In the compound represented by the general formula (L), it is more preferable that at least one of R ^L2 , R ^L3 , R ^L6 and R ^L7 is a group represented by the general formula (W).

In the compound represented by the general formula (M), R ^M2 is preferably a group represented by the general formula (W), and both R ^M2 and R ^M6 are represented by the general formula (W). More preferably, it is a group.
In the compound represented by the general formula (N), is preferably a group R ^N3 is represented by the general formula (W), both R ^N3 and R ^N9 are represented by formula (W) More preferably, it is a group.
In the compound represented by the general formula (P), R ^P3 is preferably a group represented by the general formula (W), and both R ^P3 and R ^P9 are represented by the general formula (W). More preferably, it is a group.

In the compound represented by the general formula (Q), R ^Q3 is preferably a group represented by the general formula (W), and both R ^Q3 and R ^Q9 are represented by the general formula (W). More preferably, it is a group.
In the compound represented by the general formula (R), R ^R2 is preferably a group represented by the general formula (W), and both R ^R2 and R ^R7 are represented by the general formula (W). More preferably, it is a group.

In the compound represented by the general formula (S), is preferably a group R ^S2 is represented by the general formula (W), both R ^S2 and R ^S5 is represented by the general formula (W) More preferably, it is a group.
In the compound represented by the general formula (T), R ^T2 is preferably a group represented by the general formula (W), and both R ^T2 and R ^T5 are represented by the general formula (W). More preferably, it is a group.

Of the substituents R ^{C to} R ^T , the number of substituents other than the group represented by the general formula (W) is preferably 0 to 4, and more preferably 0 to 2.

  Specific examples of the compounds represented by the general formula (C) to the general formula (T) are shown below, but the compounds that can be used in the present invention are interpreted in a limited manner by these specific examples. It shouldn't be.

  Specific examples of the compound C represented by the general formula (C) are shown.

The compound represented by the general formula (C) preferably has a molecular weight of 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and particularly preferably 850 or less. When the molecular weight is within the above range, solubility in a solvent can be enhanced.
On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 300 or more, more preferably 350 or more, and further preferably 400 or more.

  Specific examples of the compound D represented by the general formula (D) are shown.

  The upper limit of the molecular weight of the compound represented by the general formula (D) is the same as that of the compound represented by the general formula (C), so that the solubility in a solvent can be improved. On the other hand, from the viewpoint of film quality stability of the thin film, the molecular weight is preferably 400 or more, more preferably 450 or more, and further preferably 500 or more.

  Specific examples of compound E represented by general formula (E), compound F represented by general formula (F), compound G represented by general formula (G), and compound H represented by general formula (H) Examples are shown in order.

  The molecular weights of the compound E, the compound F, the compound G, and the compound H are preferably the same as the compound C whose upper limit is represented by the general formula (C), so that the solubility in a solvent can be improved. . On the other hand, from the viewpoint of film quality stability of the thin film, the lower limit of the molecular weight is the same as the compound represented by the general formula (D).

  Specific examples of Compound J and Compound K represented by General Formula (J) and General Formula (K) are shown.

  The upper limit of the molecular weights of the compound J and the compound K is the same as that of the compound C represented by the general formula (C), which is preferable because the solubility in a solvent can be increased. On the other hand, from the viewpoint of film quality stability of the thin film, the lower limit of the molecular weight is the same as the compound represented by the general formula (D).

  Compound L represented by General Formula (L), Compound M represented by General Formula (M), Compound N represented by General Formula (N), Compound P represented by General Formula (P) and General Formula Specific examples of each of the compounds Q represented by (Q) are shown in order.

  The molecular weights of the compound L, the compound M, the compound N, the compound P, and the compound Q are the same as those of the compound C represented by the general formula (C) in the upper limit, which increases the solubility in a solvent. It is possible and preferable. On the other hand, from the viewpoint of film quality stability of the thin film, the lower limit of the molecular weight is the same as the compound represented by the general formula (D).

  Specific examples of the compound R represented by the general formula (R), the compound S represented by the general formula (S), and the compound T represented by the general formula (T) are shown in order.

  The molecular weights of the compound R, the compound S, and the compound T are preferably the same as those of the compound C represented by the general formula (C), because the solubility in the solvent can be increased. On the other hand, from the viewpoint of film quality stability of the thin film, the lower limit of the molecular weight is the same as the compound represented by the general formula (D).

Examples of the organic polymer and derivatives thereof include polypyrrole and substituted products thereof, polydiketopyrrole and substituted products thereof, polythiophene and derivatives thereof, isothianaphthene such as polyisothianaphthene, thienylene vinylene such as polythienylene vinylene, poly Poly (p-phenylene vinylene) such as (p-phenylene vinylene), polyaniline and its derivatives, polyacetylene, polydiacetylene, polyazulene, polypyrene, polycarbazole, polyselenophene, polyfuran, poly (p-phenylene), polyindole, poly Examples thereof include polymers such as pyridazine, polytellurophene, polynaphthalene, polyvinylcarbazole, polyphenylene sulfide, and polyvinylene sulfide, and polymers of condensed polycyclic aromatic compounds.
Although it does not specifically limit as polythiophene and its derivative (s), For example, poly-3-hexylthiophene (P3HT) which introduce | transduced the hexyl group into polythiophene, polyethylene dioxythiophene, poly (3,4-ethylene dioxythiophene) / polystyrene sulfone An acid (PEDOT / PSS) etc. are mentioned.
Moreover, the oligomer (for example, oligothiophene) which has the same repeating unit as these polymers can also be mentioned.

Examples of the organic polymer include polymer compounds in which compounds represented by the following general formulas (C) to (T) have a repeating structure.
As such a polymer compound, the compounds represented by the general formulas (C) to (T) have a π-conjugate having a repeating structure via at least one arylene group or heteroarylene group (thiophene, bithiophene, etc.). Examples thereof include a polymer and a pendant polymer in which compounds represented by the general formulas (C) to (T) are bonded to a polymer main chain via a side chain. The polymer main chain is preferably polyacrylate, polyvinyl, polysiloxane or the like, and the side chain is preferably an alkylene group or a polyethylene oxide group. In the case of a pendant type polymer, the polymer main chain may have a group derived from a polymerizable group in which at least one of the substituents R ^{C to} R ^T is polymerized.

  These organic polymers preferably have a weight average molecular weight of 30,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more. When the weight average molecular weight is not less than the above lower limit value, the intermolecular interaction can be enhanced and high mobility can be obtained.

  In addition to the organic polymer, it is also preferable to use another resin (D). As the resin (D), polystyrene, poly α-methylstyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysilsesquioxane, polysulfone, polymethacrylate represented by polymethylmethacrylate, Insulating polymers such as polyacrylates typified by polymethyl acrylate, celluloses typified by triacetyl cellulose, polyethylene, polypropylene, polyvinyl phenol, polyvinyl alcohol, polyvinyl butyral, etc., and two or more of these components are copolymerized. And a copolymer obtained in the above manner.

  When using the resin (D), the mass ratio of the organic polymer to the total amount of the organic polymer and the resin (D) is preferably 10% by mass or more and less than 100% by mass, and preferably 20% by mass or more and less than 100% by mass. More preferred.

  In the organic semiconductor layer, the total content of the organic polymer and the resin (D) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.

When the organic semiconductor layer is formed on the gate insulating layer by a wet method (wet coating method), it is easy to obtain a high-performance OTFT at a low cost, and is also suitable for increasing the area. In addition, the gate insulating layer is formed by curing the curable composition of the present invention, and improves the applicability of the organic semiconductor material containing the organic semiconductor and enables uniform application. Therefore, the wet method is preferable as the method for forming the organic semiconductor layer.
Although it is not particularly limited as a wet method, for example, by applying an organic semiconductor material by spin coating method, ink jet method, nozzle printing, stamp printing, screen printing, gravure printing, electrospray deposition method, etc., and then drying. Can be formed.

When the organic semiconductor layer is formed on the gate insulating layer by the wet coating method, the organic semiconductor layer is preferably crystallized by heating or laser irradiation because the OTFT tends to have high performance. It is particularly preferred that the treatment has been performed.
The method for the crystallization treatment is not particularly limited, and examples thereof include heating with a hot plate and an oven or laser irradiation. As for the heating temperature, a high temperature is preferable from the viewpoint of easy crystallization, and a low temperature is preferable from the viewpoint of hardly affecting the substrate or the like. Specifically, 50 ° C. or higher is preferable, 100 ° C. or higher is particularly preferable, and on the other hand, 300 ° C. or lower is preferable, and 250 ° C. or lower is particularly preferable.

[Source electrode, drain electrode]
In the TFT of the present invention, the source electrode is an electrode through which current flows from the outside through the wiring. In addition, the drain electrode is an electrode that sends current to the outside through wiring, and is usually provided in contact with the semiconductor layer.
When the source electrode and the drain electrode are provided in contact with the gate insulating layer as shown in FIGS. 1A and 1D, the stability of the TFT characteristics is improved.
As a material of the source electrode and the drain electrode, a conductive material used in a conventional organic thin film transistor can be used, and examples thereof include the conductive material described for the gate electrode.

  The source electrode and the drain electrode can each be formed by a method similar to the method for forming the gate electrode.

As the photolithography method, a lift-off method or an etching method can be employed.
In particular, since the gate insulating layer is excellent in resistance to an etching solution and a stripping solution, the source electrode and the drain electrode can be preferably formed by an etching method. The etching method is a method of removing unnecessary portions by etching after forming a conductive material. When the patterning is performed by the etching method, the conductive material remaining on the base when the resist is removed can be peeled off, and the resist residue or the removed conductive material can be prevented from reattaching to the base, and the shape of the electrode edge portion is excellent. This is preferable to the lift-off method.

  In the lift-off method, a resist is applied to a part of the base, a conductive material is formed thereon, and the resist is removed together with the solvent by elution or peeling with a solvent. This is a method of forming a film of a conductive material only on a portion where no is applied.

Although the thickness of a source electrode and a drain electrode is arbitrary, 1 nm or more is preferable respectively and 10 nm or more is especially preferable. Moreover, 500 nm or less is preferable and 300 nm or less is especially preferable.
The interval (channel length) between the source electrode and the drain electrode is arbitrary, but is preferably 100 μm or less, and particularly preferably 50 μm or less. The channel width is preferably 5000 μm or less, and particularly preferably 1000 μm or less.

[Overcoat layer]
The TFT of the present invention may have an overcoat layer. The overcoat layer is usually a layer formed as a protective layer on the surface of the TFT. A single layer structure or a multilayer structure may be used.
The overcoat layer may be an organic overcoat layer or an inorganic overcoat layer.
The material for forming the organic overcoat layer is not particularly limited, and examples thereof include organic polymers such as polystyrene, acrylic resin, polyvinyl alcohol, polyolefin, polyimide, polyurethane, polyacetylene, and epoxy resin, and these organic polymers. Derivatives in which a crosslinkable group or a water repellent group is introduced may be mentioned. These organic polymers and derivatives thereof can be used in combination with a crosslinking component, a fluorine compound, a silicon compound, and the like.
The material for forming the inorganic overcoat layer is not particularly limited, and examples thereof include metal oxides such as silicon oxide and aluminum oxide, and metal nitrides such as silicon nitride.
These materials may be used alone or in combination of two or more in any combination and ratio.

There is no restriction | limiting in the formation method of an overcoat layer, It can form by well-known various methods.
For example, the organic overcoat layer is, for example, a solution containing a material to be an overcoat layer is applied and dried on the underlying layer, a solution containing a material to be an overcoat layer is applied, and exposure is performed after drying. It can be formed by a method such as development and patterning. The patterning of the overcoat layer can also be directly formed by a printing method, an inkjet method, or the like. The overcoat layer may be crosslinked by exposure or heating after the patterning of the overcoat layer.
On the other hand, the inorganic overcoat layer can be formed by a dry method such as a sputtering method or a vapor deposition method or a wet method such as a sol-gel method.

[Other layers]
The TFT of the present invention may be provided with layers and members other than those described above.
Examples of other layers or members include banks. The bank is used for the purpose of blocking the discharge liquid at a predetermined position when a semiconductor layer, an overcoat layer, or the like is formed by an inkjet method or the like. For this reason, the bank usually has liquid repellency. Examples of the bank forming method include a method of performing liquid repellency treatment such as a fluorine plasma method after patterning by a photolithography method or the like, a method of curing a photosensitive composition containing a liquid repellent component such as a fluorine compound, and the like.
In the case of the organic thin film transistor of the present invention, since the gate insulating layer is an organic layer, the method of curing the photosensitive composition containing the latter liquid repellent component may cause the gate insulating layer to be affected by the liquid repellent treatment. Not preferred. A technique may be used in which a liquid repellent contrast is given to the base without using the bank so as to have the same role as the bank.

[Production method]
The TFT of the present invention can be manufactured by forming or providing a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, a drain electrode, and the like on a substrate by the method described above.

  Examples of the method for applying the curable composition of the present invention include a spin casting method, a dipping method, a die coating method, a slit coating method, a dropping method, an offset or a printing method such as a screen or offset, and an ink jet method. Moreover, in order to maintain the surface smoothness of the obtained film, it is preferable to prevent mixing of impurities and the like, and it is preferable to filter with a membrane filter or the like before coating.

In the manufacture of TFT, when the curable composition of the present invention is used, and when an organic material is used as a material for forming a semiconductor layer, a TFT that exhibits excellent characteristics while taking advantage of the solution coating method is manufactured. Can do.
Further, when the curable composition of the present invention is used, a gate insulating layer that improves the coating property of the organic semiconductor material and contributes to the improvement of the stability of the TFT characteristics can be formed, and the TFT having high TFT characteristics and excellent stability. Can be produced by a solution coating method.

[Display panel]
A display panel is mentioned as an example of the use of the organic thin-film transistor of this invention. Examples of the display panel include a liquid crystal panel, an organic EL panel, and an electronic paper panel.

  The present invention will be described below in more detail based on examples, but the present invention is not limited to these examples.

[Synthesis example]
In each example, polyorganosiloxane compounds AP1 to AP10 and (tetramethylpiperidinyloxy) propylmethylsiloxane dimethylsiloxane copolymer (trade name: UBS-0822, manufactured by Gelest) were used.

(Synthesis of polyorganosiloxane compounds AP1 to AP10)
Polyorganosiloxane compound AP2 was synthesized as follows. That is, in a 500 mL three-necked flask, 100 ml of toluene, 10 g of a copolymer of polymethylhydrosiloxane and dimethylsiloxane “HMS-031” (trade name, manufactured by Gelest), 1 g of allyl methacrylate, 1.53 g of 5-vinylbenzotriazole, A 0.0186 g xylene solution of a platinum vinylsiloxane complex was added, and the reaction was carried out at 105 ° C. for 6 hours during nitrogen substitution. After confirming disappearance of the vinyl group by ¹ H-NMR, the solvent was removed by distillation under reduced pressure to obtain a polyorganosiloxane compound.
Further, the same procedure as in the synthesis of polyorganosiloxane compound AP2 except that a copolymer of polymethylhydrosiloxane and dimethylsiloxane shown in Table 1 (referred to as “copolymer” in Table 1) and a compound was used. Thus, polyorganosiloxane compounds AP1, AP3 to AP10 were synthesized.

(Synthesis of modified polyorganosiloxane compounds mAP-4 and mAP-8) 1 g of polyorganosiloxane compound AP-4 synthesized as described above, 1 g of toluene, 0.2 g of triallyl 1,3,5-benzenetricarboxylate, Then, 0.01 g of platinum vinylsiloxane complex was mixed and reacted at 100 ° C. for 5 hours. After the reaction product was cooled, the remaining toluene was removed by distillation under reduced pressure to obtain a modified polyorganosiloxane compound mAP-4.
In the same manner as in the synthesis of the modified polyorganosiloxane compound mAP-4, the reaction was performed using the polyorganosiloxane compound AP-8 to obtain a modified polyorganosiloxane compound mAP-8.

  The weight average molecular weights (Mw) of the synthesized polyorganosiloxane compounds AP1 to 3, AP5 to 7, 9 and 10, and the modified polyorganosiloxane compounds mAP-4 and mAP-8 and the content of each structural unit are as described above. Measured by the method. In the modified polyorganosiloxane compounds mAP-4 and mAP-8, the content of the structural unit in which triallyl 1,3,5-benzenetricarboxylate has reacted is represented by “e”. The measurement results are shown in Table 1.

As a polyoriganosiloxane compound for comparison, the following UMS-992, BS-1 having the following structural unit, and a mixed reaction product BS-2 of the following compound were prepared.
UMS-992: Methacryloxypropylmethylsiloxane (a = 1 mol%, b = 99 mol% or more, c = 0 mol%)

ＢＳ−１において、ａ＝２０モル％、ｂ＝２５モル％、ｃ＝５５モル％

In BS-1, a = 20 mol%, b = 25 mol%, c = 55 mol%

The mixed reaction product BS-2 was obtained as follows. That is, after putting 100 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 57.49 g of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Aldrich) into a 500 mL three-necked flask and substituting the gas phase part with nitrogen, The mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 10.0 g of triallyl isocyanuric acid, 70.0 g of toluene, and 0.0186 g of a xylene solution of platinum vinylsiloxane complex (manufactured by Aldrich) was dropped over 30 minutes. After the reaction for 6 hours, the solvent was distilled off under reduced pressure to obtain a reaction product A of polysiloxane and isocyanuric acid.
Next, 10 g of the reactant A and 20 g of toluene were placed in a 100 mL three-necked flask, and after replacing with nitrogen, the internal temperature was set to 105 ° C., and a mixed solution of 3.81 g of vinylcyclohexene oxide and 3.81 g of toluene was added dropwise over 30 minutes. After confirming disappearance of the vinyl group by ¹ H-NMR, the solvent was distilled off under reduced pressure to obtain BS-2.

[Example 1]
[Production of TFT]
A bottom gate / top contact type OTFT shown in FIG. 1B was manufactured.
A gate electrode 5 was formed on a substrate 6 made of 25 mm square non-alkali glass “Eagle XG” (trade name, manufactured by Corning) using silver nano ink (manufactured by DOWA, 40% aqueous ink).

Subsequently, 1 g of pentaerythritol tetraacrylate, 1 g of a polyorganosiloxane compound shown in Table 3, a polymerization initiator “Darocur TPO” (trade name) 0.1 g, and 2 g of dipropylene glycol monomethyl ether were mixed, and the curable composition MS- 1-14 were prepared respectively.
Each of the prepared curable compositions was applied onto the substrate 6 on which the gate electrode 5 was formed by spin coating (rotation speed: 1000 rpm, 1 minute) to form a coating film. Thereafter, the coating film was exposed for 10 seconds using a high-pressure mercury lamp 3000 mW / cm ² and cured to form a gate insulating layer 2.

  Next, on the gate insulating layer 2, a compound M3 (C8BTBT) shown below as an organic semiconductor is dissolved in toluene to prepare a toluene solution (organic semiconductor material) having an organic semiconductor concentration of 0.3% by mass. Was applied and dried by spin coating, and annealed at 130 ° C. for 2 hours to form a semiconductor layer 1.

Subsequently, as shown in FIG. 1B, the source electrode 3 and the drain electrode 4 (gate width W = 100 mm, gate length L = 100 μm) were used using silver nano ink (40% aqueous ink manufactured by DOWA), Formed.
In this manner, OTFTs (sample Nos. 1 to 12 and c1 to c3) having the structure shown in FIG.

[Evaluation of coating properties of organic semiconductors]
In manufacturing the OTFT, the formed semiconductor layer 1 was observed with an optical microscope and a polarizing microscope, and it was confirmed whether the organic semiconductor was evenly applied on the gate electrode 5 and the gate insulating layer 2. Evaluation was made with “A” indicating that the organic semiconductor was uniformly applied and “B” indicating that the organic semiconductor was biased to either the gate electrode 5 or the gate insulating layer 2. The results are shown in Table 3.

[Evaluation of wet heat stability of TFT characteristics]
Each OTFT was subjected to a moist heat resistance test to evaluate the moist heat stability of the TFT characteristics.
Specifically, a voltage of −40 V is applied between the source electrode 3 and the drain electrode 4 of each manufactured OTFT, the gate voltage Vg is changed in the range of 40 V to −40 V, and the following expression representing the drain current Id is used. The initial carrier mobility μ1 (cm ² / Vs) was calculated.

Id = (w / 2L) μCi (Vg−Vth) ²
In the formula, L is the gate length, w is the gate width, Ci is the capacitance per unit area of the gate insulating layer 2, Vg is the gate voltage, and Vth is the threshold voltage.

Next, after leaving in a wet heat environment of 40 ° C. and 50 RH% for 24 hours, the carrier mobility μ ² (cm ² / Vs) after wet heat durability was calculated in the same manner as the initial carrier mobility μ 1.
Using the obtained initial carrier mobility μ1 and carrier mobility μ2 after wet heat durability, the carrier mobility retention rate was calculated from the following formula, and the wet heat stability of the OTFT was evaluated based on the calculated value.
Carrier mobility maintenance ratio (%) = carrier mobility after wet heat durability μ2 / initial carrier mobility μ1

  The case where the carrier mobility maintenance rate (%) was 80% or more was evaluated as “A”, the case where it was 60% or more and less than 80% as “B”, and the case where it was less than 60% as “C”. The results are shown in Table 3.

As shown in Table 3, the insulation of the present invention formed from the curable composition of the present invention containing the polyorganosiloxane compound (AP) having at least the structural unit A and the structural unit B represented by the general formula (I). All the films were able to improve the coating property of the organic semiconductor material. In addition, any of the OTFTs of the present invention having this insulating film as a gate insulating layer exhibited high wet heat stability.
Thus, it was found that the curable composition of the present invention and the insulating film formed by curing the composition can improve the coating property of the organic semiconductor material and improve the wet heat stability of the TFT characteristics. Further, it has been found that the OTTF of the present invention has a semiconductor layer uniformly formed to exhibit high TFT characteristics, and has high adhesion to electrodes and the like and excellent wet heat stability of TFT characteristics.

  In particular, it was found that when the polyorganosiloxane compound (AP) has the structural unit A, the structural unit B, and the structural unit C represented by the general formula (II), the wet heat stability improvement effect is high.

  In contrast, Sample No. in which the cured product does not have a free heterocycle. In all of c1 to c3, the applicability of the organic semiconductor material was poor. Sample No. c1 was also inferior in wet heat durability.

1 Semiconductor layer (organic semiconductor layer)
2 Gate insulating layer 3 Source electrode 4 Drain electrode 5 Gate electrode 6 Substrate

Claims (15)

A thermal or photocurable composition comprising a polyorganosiloxane compound (AP) having at least a structural unit A and a structural unit B represented by the following general formula (I).

In formula ^(I), represents an alkyl group or a phenyl group having 1 to 4 carbon atoms R 1, ^{R 2} and ^{R 3} each independently. L ¹ represents a single bond or a divalent linking group. R ^x represents an aliphatic or aromatic heterocyclic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and having 3 or more carbon atoms. However, ^Rx excludes a cyanuric ring group. a and b represent the content of the structural unit A and the structural unit B in the polyorganosiloxane compound (AP), respectively, and are 1 to 99 mol%. The heat or photocurable composition according to claim 1, wherein the polyorganosiloxane compound (AP) has a structural unit A, a structural unit B, and a structural unit C represented by the following general formula (II).

In the general formula ^(II), is ^{R 1, R 2, R 3} , same meanings as ^{L 1} and ^{R R} 1 of ^x each Formula ^{(I), R 2, R} 3, L 1 and ^{R x.} R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms or a phenyl group. L ² represents a single bond or a divalent linking group, and R ^y represents a radical or a cation polymerizable functional group. a, b, and c represent the content of the structural unit A, the structural unit B, and the structural unit C in the polyorganosiloxane compound (AP), respectively, and are 1 to 98 mol%. The heat or photocurable composition according to claim 1 or 2, wherein R ^x is a nitrogen-containing aliphatic heterocycle or a nitrogen-containing aromatic heterocycle. R ^x represents a piperidine ring group, piperazine ring group, morpholine ring group, quinuclidine ring group, pyrrolidine ring group, azetidine ring group, azetidin-2-one ring group, aziridine ring group, tropane ring group, pyrrole ring group, furan Ring group, thiophene ring group, imidazole ring group, pyrazole ring group, 1,2,3-triazole ring group, 1,2,4-triazole ring group, tetrazole ring group, oxazole ring group, isoxazole ring group, thiazole ring Group, isothiazole ring group, thiadiazole ring group, phosphole ring group, pyridine ring group, pyrimidine ring group, pyridazine ring group, pyrazine ring group, 1,2,3-triazine ring group, 1,2,4-triazine ring group Quinoline ring group, isoquinoline ring group, quinazoline ring group, phthalazine ring group, pteridine ring group, coumarin ring group, chromone ring group, 1,4-benzene Nzodiazepine ring group, indole ring group, benzimidazole ring group, benzotriazole ring group, benzofuran ring group, purine ring group, acridine ring group, phenoxazine ring group, phenothiazine ring group, benzothiadiazole ring group, isobenzofuran ring group, iso Indole ring group, benzo (b) thiophene ring group, benzo (c) thiophene ring group, benzophosphole ring group, indazole ring group, benzoxazole ring group, benzoisoxazole ring group, benzothiazole ring group, quinoxaline ring group, The heat or photocurable composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of cinnoline ring groups. The thermal or photocurable composition according to any one of claims 1 to 4, wherein the ^Ry is a radical polymerizable functional group. The heat or photocurable composition according to any one of claims 1 to 5, wherein ^Ry is a (meth) acryloyloxy group or a styryl group.   At least a portion of the polyorganopolysiloxane compound (AP) has a hydrosilyl group, the hydrosilyl group of the polyorganopolysiloxane compound, and a compound (MC) having two or more alkenyl groups that do not exhibit radical polymerizability; The heat or photocurable composition according to any one of claims 1 to 6, which contains a modified polyorganosiloxane compound (mAP) obtained by reacting with.   The heat or photocurable composition according to claim 7, wherein the alkenyl group that does not exhibit radical polymerizability is a vinyl group or an allyl group.   The heat or photocurable composition according to claim 7 or 8, wherein the compound (MC) having two or more alkenyl groups that do not exhibit radical polymerizability is a polyfunctional allyl compound.   The heat or photocurable composition according to any one of claims 1 to 9, comprising a compound (B) having a radical or cationic polymerizable functional group.   The heat or photocurable composition according to claim 10, wherein the compound (B) is a compound having a radical polymerizable functional group.   The heat or photocurable composition according to any one of claims 1 to 11, comprising a heat or photopolymerization initiator.   The insulating film formed by hardening | curing the heat | fever or photocurable composition of any one of Claims 1-12.   A thin film transistor having the insulating film according to claim 13 as a gate insulating layer. The thin film transistor according to claim 14, wherein the gate insulating layer is provided between a gate electrode and a semiconductor layer provided on the gate electrode.

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