JP2013225639A - Organic film manufacturing method, organic film obtained therewith, and electronic device and field effect transistor including organic film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control crystallinity of formed thin film by use of energy difference among elimination reaction of solvent-soluble detachable substituents of a plurality of π-electron conjugated compound precursors.SOLUTION: An organic film manufacturing method includes converting, as shown in the specified general formula (I), a coating, formed by applying a coating liquid containing at least two or more π-electron conjugated compound precursors A-(Bn)m, into a single π-electron conjugated compound A-(C)m and leaving substituents X-Y.

Description

  The present invention relates to a method for producing an organic film made of a π-electron conjugated compound, an electronic device using the organic film obtained thereby, and a field effect transistor.

In recent years, research and development of organic thin film transistors using organic semiconductor materials has been active.
So far, acene-based materials such as pentacene have been reported as organic semiconductor materials of low-molecular derivatives (see, for example, Patent Document 1 and Non-Patent Document 1).
Organic thin-film transistors using pentacene as an organic semiconductor layer have been reported to have a relatively high mobility, but these acene-based materials have extremely low solubility in general-purpose solvents. When thinning as a layer, it is necessary to go through a vacuum deposition process. Therefore, it does not meet the expectation for an organic semiconductor material that a thin film can be formed by a simple process such as coating and printing as described above.

Furthermore, as one of the acene-based materials similar to pentacene, for example, 2,7-diphenyl [1] benzothieno having a structure represented by the following formula (1) which is a derivative of benzothieno [3,2-b] benzothiophene [3,2-b] [1] benzothiophene (refer to Patent Document 2 and Non-Patent Document 2) is deposited on a substrate treated with octadecyltrichlorosilane, whereby mobility comparable to that of pentacene (about 2.0 cm). ² / V · s) and long-term stability in the atmosphere. However, this compound, like pentacene, needs to go through a vacuum deposition process, and does not meet the expectation for an organic semiconductor material that a thin film can be formed by a simple process such as coating or printing.

  By the way, an organic semiconductor material can be easily formed into a thin film by a simple method using a wet process such as a printing method, a spin coating method, or an ink jet method, and the manufacturing process temperature is lower than that of a thin film transistor using a conventional inorganic semiconductor material. There is an advantage that the temperature can be lowered. As a result, it can be formed on plastic substrates with low heat resistance in general, and electronic devices such as displays can be reduced in weight and cost, and various developments such as applications that take advantage of the flexibility of plastic substrates are expected. it can.

Therefore, it has liquid crystallinity, high solvent solubility, can be applied by spin coating, casting, etc., and has a mobility comparable to that of pentacene by heat treatment at a liquid crystal phase temperature (about 100 ° C.) or less. 2,7-dialkyl [1] benzothieno [3,2-b] [1] benzothiophene having the structure represented by the following formula (2), which is the same derivative showing about 2.0 cm ² / V · s) It has been proposed to use the method (see Patent Document 2 and Non-Patent Document 3). However, in this case, the temperature at which the liquid crystal phase is developed is relatively low at about 100 ° C., and the film structure can be changed by heat treatment even after film formation.

  Therefore, in recent years, a low molecular weight compound having high solvent solubility is used as a semiconductor precursor, and this is dissolved in a solvent and formed into a film by a coating process, and then converted into a semiconductor to obtain an organic semiconductor film. In recent years, a method for producing the above has been reported. For example, methods of converting to pentacene, porphyrin-based compounds, and phthalocyanine-based compounds using retro Diels-Alder reaction have been energetically studied (see, for example, Patent Documents 3 to 9 and Non-Patent Documents 4 to 7). .

  As described in Non-Patent Document 4, the charge mobility in an organic semiconductor material depends on the regular molecular arrangement (ordering such as crystallization) of the organic material film. While it is possible to ensure the molecular alignment of the material therein, organic materials having molecular alignment are generally less soluble in organic solvents. In other words, the semiconductor characteristics of the organic material film and the film forming ease (depending on the coating method) are generally incompatible. Therefore, the only way to make both compatible is to convert the precursor in the coating into an organic semiconductor material after forming the coating with a coating solution using a semiconductor precursor having a group soluble in the solvent. Can be considered.

  However, among these examples, tetrachlorobenzene molecules and the like are eliminated from the pentacene precursor, but tetrachlorobenzene has a high boiling point and is difficult to remove out of the reaction system, and its toxicity is a concern. In addition, both porphyrin and phthalocyanine require complicated synthesis, so the application range is narrow, and the development of a π-electron conjugated compound precursor (semiconductor precursor having a soluble group) that can be synthesized more easily is necessary. Has been.

In addition, a method has been proposed in which a solvent-soluble precursor having a sulfonate ester-based substituent is externally stimulated to eliminate the substituent and replace it with a hydrogen atom to convert it into phthalocyanine ( For example, refer to Patent Documents 10 and 11).
However, this method has a problem that the sulfonic acid ester has a high polarity, so the solubility in a non-polar organic solvent is not sufficient, and the temperature required for the conversion from the precursor is relatively high at least 250 ° C. to 300 ° C. Met.

In addition, olefinic oligothiophene and olefin substituted [1] benzothieno [3] are obtained by solubilizing by introducing a carboxylate having an alkyl chain at the molecular terminal β-position of oligothiophene and removing it by applying heat. , 2-b] [1] benzothiophene has been proposed (see, for example, Patent Documents 12 and 13 and Non-Patent Document 7). In this method, it is reported that desorption occurs by heating at about 150 ° C. to 250 ° C.
Furthermore, the present inventors can eliminate a substituent if it is a substituent elimination compound (precursor) based on a cyclohexene skeleton having an acyloxy group (specifically, a carboxylic acid ester) structure as a leaving group. Since the latter structure is not an olefin group as described above (olefin-substituted oligothiophene or olefin-substituted [1] benzothieno [3,2-b] [1] benzothiophene) but a benzene ring, cis-trans isomerization can be achieved. A more advantageous method has been found in that it does not occur and has already been disclosed in Patent Document 14.
Furthermore, a thin film formed by converting these detachable soluble groups by an external stimulus spontaneously forms a crystal or an amorphous film by an elimination reaction accompanying the external stimulus. Therefore, the crystallinity of the formed thin film cannot be controlled intentionally. Therefore, there are problems such as a decrease in film formability due to a difference in surface energy between the compound after conversion and the substrate, and control of the size of the crystal domain.

  The present invention has been made in view of the current state of the prior art described above, and is a thin film formed by utilizing the energy difference in the elimination reaction of a solvent-soluble substituent capable of detaching a plurality of π-electron conjugated compound precursors. It aims at controlling the crystallinity of.

The above-described problems are solved by the present invention including the following “organic film”, “organic film manufacturing method”, and “organic electronic device”.
(1) “As shown in the following general formula (I), a coating film formed by applying a coating liquid containing at least two or more π-electron conjugated compound precursors A- (Bn) m” , a method of manufacturing an organic film which comprises a step of converting a single π-electron conjugated compound A- (C) m and leaving substituent X _n -Y _n;

（ここでＡはπ電子共役系置換基であり、Ｂ_ｎは上記一般式（II）で表される構造を少なくとも部分構造として有している溶媒可溶性置換基である。ｎは前記溶媒可溶性置換基の種類を表わす２以上の自然数であり、ｍは前記溶媒可溶性置換基に結合する脱離性置換基数を表わす自然数である。Ｃは上記一般式（III）で示されている構造を少なくとも部分構造として有している。Ｒ_１からＲ_３は水素原子または置換基であり、互いに環状を形成していてもよく、Ａと共有結合を介して環状を形成していてもよい。
上記一般式（Ｉ）及び（II）中、Ｘ_ｎ，Ｙ_ｎのうち一方は水素原子、他方は脱離性置換基を表し、ｍ≧２の場合、Ｘ_ｎまたはＹ_ｎの脱離性置換基は互いに同一であっても異なっていても良く、環状の前記脱離性置換基を形成していても良い。ただし、Ｂ_ｎは上記一般式（Ｉ）中、Ａ上の任意の原子と共有結合を介して連結している。）」。

(Here, A is a π-electron conjugated substituent, and B _n is a solvent-soluble substituent having at least a partial structure having the structure represented by the general formula (II). N is the solvent-soluble substituent. A natural number of 2 or more representing the type of group, m is a natural number representing the number of detachable substituents bonded to the solvent-soluble substituent, and C is at least part of the structure represented by the general formula (III). R ₁ to R ₃ are a hydrogen atom or a substituent, and may form a ring with each other, or may form a ring with A through a covalent bond.
In the general formulas (I) and (II), one of X _n and Y _n represents a hydrogen atom and the other represents a detachable substituent. When m ≧ 2, detachable substitution of X _n or Y _n The groups may be the same as or different from each other, and may form the cyclic leaving substituent. However, _Bn is linked to any atom on A in the above general formula (I) via a covalent bond. ) "

(2) In the above item (1), wherein the leaving substituent X _n or Y _n is an optionally substituted [ether group or acyloxy group] having 1 or more carbon atoms The manufacturing method of the organic film of description. "
(3) “the π-electron conjugated substituent A is (i) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound residue in which two or more of the rings are condensed, and (Ii) The item (1) or (1) above, which is a π-electron conjugated compound residue selected from the group consisting of compound residues in which the rings in (i) are linked via a covalent bond The manufacturing method of the organic film as described in 2). "
(4) “π-electron conjugated compound wherein the substituent A is selected from a condensed compound residue selected from a thiophene ring and a benzene ring or a compound residue in which the rings of the compound are linked via a covalent bond The method for producing an organic film according to any one of (1) to (3), which is a residue.
(5) “An organic film obtained by the manufacturing method according to any one of items (1) to (4)”.
(6) "Organic electronic device using the organic film as described in the above item (5)."
(7) “The organic electronic device according to (6), wherein the organic electronic device is a field effect transistor.”

  As will be understood from the following detailed and specific description, according to the present invention, using the energy difference of the elimination reaction of the solvent-soluble substituents capable of detaching a plurality of π-electron conjugated compound precursors, By controlling the crystallinity of the formed thin film, an extremely excellent effect that an organic material film excellent in semiconductor characteristics can be easily formed by, for example, a coating method is exhibited.

It is a figure which shows IR spectrum of 170,180,220,230,240,260 degreeC and (pi) electron conjugated compound (2) before the heating of (pi) electron conjugated compound precursor (1) used by this invention. It is a result of the thermal decomposition behavior (TGDTA) of the π-electron conjugated compound precursor (1) used in the present invention. The single crystal of the π-electron conjugated compound (5) used in the present invention is observed with a polarizing microscope (parallel Nicol). It is a SEM photograph of pi electron conjugated compound (5) obtained by converting pi electron conjugated compound precursor (4) used by the present invention. It is a SEM photograph of the vacuum-deposited film | membrane of the (pi) electron conjugated compound (5) used by this invention. It is a microscope observation photograph of the (pi) electron conjugated compound (5) obtained by converting the mixed film of (pi) electron conjugated compound precursor (9) and (11). It is a microscope observation photograph of the π-electron conjugated compound (5) obtained by converting a single film of the π-electron conjugated compound precursor (9). It is a microscope observation photograph of the (pi) electron conjugated compound (5) obtained by converting the single film | membrane of (pi) electron conjugated compound precursor (11). It is a result of the thermal analysis (TG) of TGDTA of a pi electron conjugated compound precursor (4). It is the result of the thermal analysis (TG) of TGDTA of a pi electron conjugated compound precursor (13). It is a microscope observation photograph of the π-electron conjugated compound (5) obtained by converting the mixed film of the π-electron conjugated compound precursor (4:10 wt%) and the π-electron conjugated compound precursor (13:90 wt%). It is a microscope observation photograph of the π-electron conjugated compound (5) obtained by converting the mixed film of the π-electron conjugated compound precursor (4:50 wt%) and the π-electron conjugated compound precursor (13:50 wt%). It is a microscope observation photograph of the π-electron conjugated compound (5) obtained by converting the mixed film of the π-electron conjugated compound precursor (4:90 wt%) and the π-electron conjugated compound precursor (13:10 wt%). It is a microscope observation photograph of the π-electron conjugated compound (5) obtained by converting the mixed film of the π-electron conjugated compound precursor (4:99 wt%) and the π-electron conjugated compound precursor (13: 1 wt%). It is a microscope observation photograph of the pi-electron conjugated compound (5) obtained by converting a single film of the pi-electron conjugated compound precursor (4). It is the schematic of the organic thin-film transistor which has the organic film obtained by this invention.

  Hereinafter, the present invention will be described with reference to embodiments. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist thereof.

  Here, the π-electron conjugated compound precursor used in the present invention and the π-electron conjugated compound obtained from the compound will be specifically described.

[Π-electron conjugated compound precursor and π-electron conjugated compound obtained from the compound]
The feature of the π-electron conjugated compound used in the present invention is that a π-electron conjugated compound precursor having a specific solvent-soluble substituent is subjected to external stimulation to release a specific substituent. It is characterized in that an electron conjugated compound can be obtained, and the π electron conjugated compound precursor is simply expressed as a precursor. The “π-electron conjugated compound precursor” is represented by A- (B _n ) m. That is, A is a π-electron conjugated substituent, and B _n is a solvent-soluble substituent having at least a partial structure represented by the general formula (II). m is a natural number representing the number of leaving substituents bonded to the solvent-soluble substituent. However, B _n is linked to any atom on A except the carbon atom at the substitution position of X _n or Y _{n in} the general formula (I) through a covalent bond, or a π-electron conjugated substituent A forming any carbon atoms and a cyclic excluding carbon atoms of the substitution position of leaving substituent X _n or Y _n above.
By applying an external stimulus to this, the solvent-soluble substituent B _n is a substitution in which specific leaving substituents X _n and Y _n are eliminated in the form of X _n Y _n , and partly reduced to olefins instead. A π-electron conjugated compound represented by the π-electron conjugated compound A- (C) m of the general formula (II) is obtained while being converted to the group C.
The π-electron conjugated compound precursor used in the present invention has a structure in which a solvent-soluble substituent _Bn is bonded to A which is a π-electron conjugated substituent.

Here, the solvent-soluble substituent _Bn and the substituent C are represented by the following general formulas (II) and (III).

（ここでＡはπ電子共役系置換基であり、Ｂ_ｎは上記一般式（II）で表される構造を少なくとも部分構造として有している溶媒可溶性置換基である。ｎは前記溶媒可溶性置換基の種類番号を表わす２以上の自然数であり，ｍは前記溶媒可溶性置換基に結合する脱離性置換基数を表わす自然数である。Ｃは上記一般式（III）で示されている構造を少なくとも部分構造として有している。Ｒ_１からＲ_３は水素原子または置換基であり、互いに環状を形成していてもよく、Ａと共有結合を介して環状を形成していてもよい。
上記一般式（Ｉ）及び（II）中、Ｘ_ｎ，Ｙ_ｎのうち一方は水素原子、他方は脱離性置換基を表し、ｍ≧２の場合、Ｘ_ｎまたはＹ_ｎの脱離性置換基は互いに同一であっても異なっていても良く、環状の前記脱離性置換基を形成していても良い。ただし、Ｂ_ｎは上記一般式（Ｉ）中、原子と共有結合を介して連結している。）

(Here, A is a π-electron conjugated substituent, and B _n is a solvent-soluble substituent having at least a partial structure having the structure represented by the general formula (II). N is the solvent-soluble substituent. A natural number of 2 or more representing the type number of the group, m is a natural number representing the number of leaving substituents bonded to the solvent-soluble substituent, and C represents at least the structure represented by the general formula (III). R ₁ to R ₃ are each a hydrogen atom or a substituent, and may form a ring with each other, or may form a ring with A through a covalent bond.
In the general formulas (I) and (II), one of X _n and Y _n represents a hydrogen atom and the other represents a detachable substituent. When m ≧ 2, detachable substitution of X _n or Y _n The groups may be the same as or different from each other, and may form the cyclic leaving substituent. However, _Bn is connected to the atom through a covalent bond in the above general formula (I). )

_{"X n} group and _{Y n} group"
In the above formulas (I) and (II), the group represented by X _n and Y _n is a hydrogen atom or a detachable substituent [that is, an optionally substituted ether group, acyloxy group having 1 or more carbon atoms] Or an optionally substituted sulfonyloxy group, etc.], and at least one of X _n and Y _n is a leaving substituent, and the other is a hydrogen atom. The leaving substituent is preferably a substituted or unsubstituted ether group, an acyloxy group, or a sulfonyloxy group. Of these, a substituted or unsubstituted ether group or a substituted or unsubstituted acyloxy group is more preferred, and a substituted or unsubstituted ether group. Substituted acyloxy groups are particularly preferred.
The ether group having 1 or more carbon atoms which may be substituted is derived from an alcohol such as a linear or cyclic aliphatic alcohol having 1 or more carbon atoms or an aromatic alcohol having 4 or more carbon atoms. Of ether groups. Further, a thioether group in which an oxygen atom in the ether is replaced with a sulfur atom can also be included. Specifically, for example, methoxy group, ethoxy group, propoxy group, butoxy group, isobutoxy group, pivaloyl group, pentoxy group, hexyloxy group, lauryloxy group, trifluoromethoxy group, 3,3,3-trifluoropropoxy group, Pentafluoropropoxy group, cyclopropoxy group, cyclobutoxy group, cyclohexyloxy group, trimethylsilyloxy group, triethylsilyloxy group, tert-butyldimethylsilyloxy group, tert-butyldiphenylsilyloxy group, etc. Corresponding thioethers in which oxygen is replaced with sulfur are also included.

  Examples of the acyloxy group having 1 or more carbon atoms which may be substituted include a formyloxy group, a linear or cyclic aliphatic carboxylic acid and carbonic acid half ester which may contain a halogen atom having 2 or more carbon atoms, carbon Examples thereof include acyloxy groups derived from carboxylic acids and carbonic acid half esters such as aromatic carboxylic acids having a number of 4 or more. Moreover, thiocarboxylic acid in which the oxygen atom of the carboxylic acid is replaced with sulfur can also be included. Specifically, for example, formyloxy group, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, pentanoyloxy, hexanoyloxy, lauroyloxy group, stearoyloxy group, trifluoroacetyloxy 3,3,3-trifluoropropionyloxy, pentafluoropropionyloxy, cyclopropanoyloxy, cyclobutanoyloxy, cyclohexanoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, pentafluorobenzoyloxy group Etc. In addition, a carbonic acid ester derived from a carbonic acid half ester in which an oxygen atom or a sulfur atom is inserted between the carbonyl group of the acyloxy group exemplified above and an alkyl group or an aryl group can also be mentioned. In addition, corresponding acylthiooxy compounds and thioacyloxy compounds in which one or more of oxygen at the ether bond site and the carbonyl site are replaced with sulfur are also included.

  Examples of the optionally substituted sulfonyloxy group include a sulfonyloxy group derived from a sulfonic acid such as a linear or cyclic aliphatic sulfonic acid having 1 or more carbon atoms and an aromatic sulfonic acid having 4 or more carbon atoms. Specifically, for example, methylsulfonyloxy group, ethylsulfonyloxy group, isopropylsulfonyloxy group, pivaloylsulfonyloxy group, pentanoylsulfonyloxy group, hexanoylsulfonyloxy group, trifluoromethanesulfonyloxy group, 3, 3 , 3-trifluoropropionylsulfonyloxy group, phenylsulfonyloxy group, p-toluenesulfonyloxy group, and the like, and a sulfonylthiooxy group in which the oxygen atom of the ether moiety is replaced with a sulfur atom can also be included.

By introducing the detachable substituents Xn and Yn (an optionally substituted ether group having 1 or more carbon atoms, acyloxy group, etc.) used in the present invention, high solubility in an organic solvent and stability of a compound skeleton are obtained. The leaving group can be eliminated while maintaining.
To illustrate some of the leaving substituent X _n and Y _n of the concepts in the following.

“R ₁ group to R ₃ group”
In addition, as described above, the group represented by R _{1 to} R ₃ in the present invention includes a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or a monovalent organic compound. Group (however, in R _{1 to} R ₃ , a monovalent organic group other than an ether group or an acyloxy group having 1 or more carbon atoms which may be substituted) is used. As the monovalent organic group, an alkyl group is used. Group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxyl group, thioalkoxyl group, aryloxy group, thioaryloxy group, heteroaryloxy group, heteroarylthiooxy group, cyano group, hydroxyl group, nitro group , Carboxyl group, thiol group, amino group and the like.

The alkyl group represents a linear or branched or cyclic substituted or unsubstituted alkyl group.
Examples thereof include alkyl groups [preferably substituted or unsubstituted alkyl groups having 1 or more carbon atoms [for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group]. Group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group]], cycloalkyl group [preferably A substituted or unsubstituted alkyl group having 3 or more carbon atoms [eg, cyclopentyl group, cyclo Butyl group, a cyclohexyl group, pentafluoro cyclohexyl]] and the like.
In other monovalent organic groups described below, the alkyl group represents an alkyl group of the above concept.

  The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Examples thereof include an alkenyl group [preferably a substituted or unsubstituted alkenyl group having 2 or more carbon atoms, and one or more double bonds of any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. [For example, ethenyl group (vinyl group), propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group Group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 1-octenyl group, 2-octenyl group Group, 3-octenyl group, 4-octenyl group, 1,1,1-trifluoro-2-butenyl group]. ], A cycloalkenyl group [which includes one or more double bonds of any carbon-carbon single bond of the cycloalkyl group having 2 or more carbon atoms described above [for example, 1-cycloallyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group 4-cycloheptenyl group, 3-fluoro-1-cyclohexenyl group]. ] Etc. are mentioned. The alkenyl group may be any of stereoisomers such as trans (E) isomer and cis (Z) isomer, and may be a mixture composed of any ratio thereof. .

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 or more carbon atoms, wherein one or more triple bonds are formed from any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. Can be mentioned. Examples of such alkynyl groups include ethynyl group, propargyl group, trimethylsilylethynyl group, and triisopropylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 or more carbon atoms [for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-chlorophenyl, p-fluorophenyl, p-trifluoro. Phenyl, naphthyl, etc.].

  The heteroaryl group is preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound [for example, 2-furyl, 2-thienyl, 3-thienyl, 2-thienothienyl. , 2-benzothienyl, 2-pyrimidyl, etc.].

  The alkoxyl group and thioalkoxyl group are preferably substituted or unsubstituted alkoxyl groups and thioalkoxyl groups, and an oxygen atom or a sulfur atom is inserted at the bonding position of the alkyl group, alkenyl group, and alkynyl group exemplified above. Specific examples thereof include alkoxy groups or thioalkoxy groups.

  The aryloxy group and thioaryloxy group are preferably a substituted or unsubstituted aryloxy group and an arylthiooxy group, and an aryl or oxygen atom is inserted into the aryl group binding site exemplified above. Specific examples include an oxy group or a thioalkoxy group.

  The heteroaryloxy group and heterothioaryloxy group are preferably a substituted or unsubstituted heteroaryloxy group and heteroarylthiooxy group, and an oxygen atom or a sulfur atom at the binding site of the heteroaryl group exemplified above. Specific examples include those in which a heteroaryloxy group or a heteroarylthioaryloxy group is inserted.

  The amino group is preferably an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group [for example, an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group. Group, diphenylamino group], acylamino group [preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, [for example, formylamino, acetylamino, pivaloylamino group, lauroyl Amino, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group]], aminocarbonylamino group [preferably carbon-substituted or unsubstituted aminocarbonylamino group, [for example, carbamoylamino group] , N, N-Dime Le aminocarbonylamino group, N, N-diethylamino carbonyl amino group, a morpholinocarbonylamino group]], and the like.

The π-electron conjugated substituent A may be any as long as it has a π-electron conjugated plane, and specifically includes a benzene ring, a thiophene ring, a pyridine ring, a benzene ring, a pyridine ring, and a pyrazine. Those having a ring, a pyrimidine ring, a triazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a furan ring, a thiophene ring, a selenophene ring, and a silole ring are more preferable,
(I) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound residue in which the rings are condensed;
(Ii) a compound residue in which the rings in (i) are linked via a covalent bond,
A π-electron conjugated compound residue selected from a combination selected from at least one selected from the group formed by (i) and (ii) above is preferred, and the aromatic hydrocarbon ring or aromatic heterocycle thereof is respectively It is preferable that the π electron possessed has a structure that is delocalized in the condensed ring or the entire linking ring by the interaction due to the linking via the condensed ring and the covalent bond.
Examples of the covalent bond here include a carbon-carbon single bond, a carbon-carbon double bond, a carbon-carbon triple bond, an oxyether bond, a thioether bond, an amide bond, and an ester bond. , Either a double bond or a triple bond.
The number of aromatic hydrocarbon rings or aromatic heterocycles linked by a condensed ring or a covalent bond is preferably 2 or more. Specific examples (general formulas are given for some examples) include naphthalene, anthracene, tetracene (also known as naphthacene), chrysene, pyrene [the following general formula (Ar3)], pentacene, thienothiophene [the following general formula (Ar1) )], Thienodithiophene, triphenylene, hexabenzocoronene, benzothiophene [the following general formula (Ar2)], benzodithiophene, [1] benzothieno [3,2-b] [1] benzothiophene [B _n TB _n T The following general formula (Ar4)], dinaphtho [2,3-b: 2 ′, 3′-f] [3,2-b] thienothiophene [DNTT], benzodithienothiophene [TTPTT; )], Naphthodithienothiophene [TTNTTT; residues of condensed polycyclic compounds such as the following general formulas (Ar6) and (Ar7)], bif Cycloalkenyl, terphenyl, quarter phenyl, bithiophene, aromatic hydrocarbon rings and aromatic heterocyclic residues oligomers such as terthiophene, quaterthiophene, phthalocyanines, residues of porphyrins, and the like. The following general formulas (Ar1) to (Ar7) are divalent residues, but in the present invention, of course, not only divalent residues but also monovalent ones or more polyvalent ones. Residues can be used. )

The solvent-soluble substituent _Bn is not particularly limited as long as it partially includes the structure represented by the general formula (II).

The following compound precursor group is exemplified as a specific structure of A- (B _n ) m that can be obtained by combining the above-described π-electron conjugated substituent A and the solvent-soluble substituent B _n. The electron conjugated compound precursor is not limited to these. Moreover, it can be easily inferred that a plurality of acyloxy group stereoisomers exist in the solvent-soluble substituent _Bn , and it is also inferred that the following compound precursor is a mixture of isomers having different steric configurations.

By applying external energy to the precursor A- (B _n ) m, a desorption reaction described later is caused, and a specific substituent is eliminated, whereby a π-electron conjugated compound A- (C) m is obtained. It is possible to obtain a film-like body containing the compound as well as the compound.
Specific examples of A- (C) m produced from A- (B _n ) m shown in the specific examples are shown below, but the π-electron conjugated compounds in the present invention are limited to these. is not.

Furthermore, in the solvent-soluble substituent B _n , R ₁ to R ₃ can form a ring with each other. When m ≧ 2, a preferable example of forming a ring includes a structure partially having a cyclohexene structure. . In this case, the general formulas (I), (II), and (III) can be expressed as the following general formulas (IV), (V), and (VI), respectively.

（ここでＡはπ電子共役系置換基であり、Ｂ’_１、Ｂ’_２、・・Ｂ_ｎ’は上記一般式（IV）で表される構造を少なくとも部分構造として有している溶媒可溶性置換基である。ｍは自然数である。
ただし、Ｂ’_１、Ｂ’_２、・・Ｂ_ｎ’は上記一般式（IV）中、（Ｘ_ｎ１，Ｘ_ｎ２），（Ｙ_ｎ１，Ｙ_ｎ２）の置換位置の炭素原子を除くＡ上の任意の原子と共有結合を介して連結しているか、Ａ上の（Ｘ_ｎ１，Ｘ_ｎ２），（Ｙ_ｎ１，Ｙ_ｎ２）の置換位置の炭素原子を除く任意の炭素原子と縮環している。Ｃ’は上記一般式（VI）で表される構造を少なくとも部分構造として有している。
上記一般式（IV）および（Ｖ）中、（Ｘ_ｎ１，Ｘ_ｎ２）、（Ｙ_ｎ１，Ｙ_ｎ２）のうち少なくともいずれか一対はともに水素原子であり、残りの一対はともに置換または無置換の炭素数１以上のアシルオキシ基である。また、（Ｘ_ｎ１，Ｘ_ｎ２）または（Ｙ_ｎ１，Ｙ_ｎ２）の一対の前記アシルオキシ基は互いに同一であっても異なっていても良く、環状の前記アシルオキシ基を形成していても良い。Ｒ_６乃至Ｒ_９は水素原子または置換基である。）
ただし、（Ｘ_ｎ１，Ｘ_ｎ２）が前記アシルオキシ基であるとき、（Ｙ_ｎ１，Ｙ_ｎ２）は水素原子であり、（Ｙ_ｎ１，Ｙ_ｎ２）が前記アシルオキシ基であるとき（Ｘ_ｎ１，Ｘ_ｎ２）は水素原子である。
さらに、一般式（IV）中、構造Ｂ’_ｎの一例としては下記の様な構造が挙げられるが、但し、これらは一部の例であって、本発明は、これら例に限られない（これら例は１価の置換基であるが、本発明は多価の置換基の場合を除外する理由がない）。

(Wherein A is a π-electron conjugated substituent, and B ′ ₁ , B ′ ₂ ,... B _n ′ are solvent-soluble having at least a partial structure of the structure represented by the general formula (IV). M is a natural number.
However, B ′ ₁ , B ′ ₂ ,... B _n ′ are on A except the carbon atom at the substitution position of (X _n1 , X _n2 ), (Y _n1 , Y _n2 ) in the general formula (IV). It is connected to any atom through a covalent bond, or is fused with any carbon atom except the carbon atom at the substitution position of (X _n1 , X _n2 ), (Y _n1 , Y _n2 ) on A . C ′ has at least a partial structure of the structure represented by the general formula (VI).
In the general formulas (IV) and (V), at least one pair of (X _n1 , X _n2 ) and (Y _n1 , Y _n2 ) is both a hydrogen atom, and the remaining pairs are both substituted or unsubstituted. An acyloxy group having 1 or more carbon atoms. The pair of acyloxy groups of (X _n1 , X _n2 ) or (Y _n1 , Y _n2 ) may be the same as or different from each other, and may form the cyclic acyloxy group. R _{6 to} R ₉ are a hydrogen atom or a substituent. )
_{However, (X n1,} X _n2) time is said acyloxy _{group, (Y n1,} Y _n2) is a hydrogen _{atom, (Y n1,} Y _n2) time is the said acyloxy group _{(X n1,} X _n2 ) Is a hydrogen atom.
Furthermore, in the general formula (IV), examples of the structure B ′ _n include the following structures, but these are only some examples, and the present invention is not limited to these examples ( These examples are monovalent substituents, but there is no reason to exclude the case of multivalent substituents in the present invention).

These are linked to the π-electron conjugated substituent A via a condensed ring or a covalent bond, except for carbon atoms at the substitution positions of R _{6 to} R ₉ and (X _n1 , X _n2 ) and (Y _n1 , Y _n2 ) Can be done.

The following compound precursor group is exemplified as a specific structure of A- (B _n ) m that can be obtained by combining the above-described π-electron conjugated substituent A and the solvent-soluble substituent B _n. The electron conjugated compound precursor is not limited to these. Moreover, it can be easily inferred that a plurality of acyloxy group stereoisomers exist in the solvent-soluble substituent _Bn , and it is also inferred that the following compound precursor is a mixture of isomers having different steric configurations.

By applying external energy to the precursor A- (B _n ) m, a desorption reaction described later is caused, and a specific substituent is eliminated, whereby a π-electron conjugated compound A- (C) m is obtained. It is possible to obtain a film-like body containing the compound as well as the compound.
Specific examples of A- (C) m produced from A- (B _n ) m shown in the specific examples are shown below, but the π-electron conjugated compounds in the present invention are limited to these. is not.

In addition, in the solvent-soluble substituent B _n , R ₁ to R ₃ can form a ring with each other, and a preferable example of forming a ring includes a structure partially having a cyclohexadiene structure. In this case, the general formulas (I), (II), and (III) can be expressed as the following general formulas (VII), (VIII), and (IX), respectively.

The groups represented by Q _{1 to} Q ₆ are defined in the same manner as R _{1 to} R _3, and are a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or Monovalent organic groups are mentioned (however, Q2 to Q5 may be a monovalent organic group residue constituting a part of the ring structure together with adjacent groups). , Alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxyl group, thioalkoxyl group, aryloxy group, thioaryloxy group, heteroaryloxy group, heteroarylthiooxy group, cyano group, hydroxyl group, Examples thereof include a nitro group, a carboxyl group, a thiol group, and an amino group.

The alkyl group represents a linear or branched or cyclic substituted or unsubstituted alkyl group.
Examples thereof include alkyl groups [preferably substituted or unsubstituted alkyl groups having 1 or more carbon atoms [for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group]. Group, n-butyl group, i-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, trifluorooctyl group, trifluorododecyl group, trifluorooctadecyl group, 2-cyanoethyl group]], cycloalkyl group [preferably A substituted or unsubstituted alkyl group having 3 or more carbon atoms [eg, cyclopentyl group, cyclo Butyl group, a cyclohexyl group, pentafluoro cyclohexyl]] and the like.
In other monovalent organic groups described below, the alkyl group represents an alkyl group of the above concept.

  The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Examples thereof include an alkenyl group [preferably a substituted or unsubstituted alkenyl group having 2 or more carbon atoms, and one or more double bonds of any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. [For example, ethenyl group (vinyl group), propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 2-methyl-2-butenyl group, 1-pentenyl group, 2-pentenyl group Group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 1-octenyl group, 2-octenyl group Group, 3-octenyl group, 4-octenyl group, 1,1,1-trifluoro-2-butenyl group]. ], A cycloalkenyl group [which includes one or more double bonds of any carbon-carbon single bond of the cycloalkyl group having 2 or more carbon atoms described above [for example, 1-cycloallyl group, 1-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group 4-cycloheptenyl group, 3-fluoro-1-cyclohexenyl group]. ] Etc. are mentioned. The alkenyl group may be any of stereoisomers such as trans (E) isomer and cis (Z) isomer, and may be a mixture composed of any ratio thereof. .

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 or more carbon atoms, wherein one or more triple bonds are formed from any carbon-carbon single bond of the above-described alkyl group having 2 or more carbon atoms. Can be mentioned. Examples of such alkynyl groups include ethynyl group, propargyl group, trimethylsilylethynyl group, and triisopropylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 or more carbon atoms [for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-chlorophenyl, p-fluorophenyl, p-trifluoro. Phenyl, naphthyl, etc.].

  The heteroaryl group is preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound [for example, 2-furyl, 2-thienyl, 3-thienyl, 2-thienothienyl. , 2-benzothienyl, 2-pyrimidyl, etc.].

  The alkoxyl group and thioalkoxyl group are preferably substituted or unsubstituted alkoxyl groups and thioalkoxyl groups, and an oxygen atom or a sulfur atom is inserted at the bonding position of the alkyl group, alkenyl group, and alkynyl group exemplified above. Specific examples thereof include alkoxy groups or thioalkoxy groups.

  The aryloxy group and thioaryloxy group are preferably a substituted or unsubstituted aryloxy group and an arylthiooxy group, and an aryl or oxygen atom is inserted into the aryl group binding site exemplified above. Specific examples include an oxy group or a thioalkoxy group.

  The heteroaryloxy group and heterothioaryloxy group are preferably a substituted or unsubstituted heteroaryloxy group and heteroarylthiooxy group, and an oxygen atom or a sulfur atom at the binding site of the heteroaryl group exemplified above. Specific examples include those in which a heteroaryloxy group or a heteroarylthioaryloxy group is inserted.

  The amino group is preferably an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted anilino group [for example, an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group. Group, diphenylamino group], acylamino group [preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group, [for example, formylamino, acetylamino, pivaloylamino group, lauroyl Amino, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group]], aminocarbonylamino group [preferably carbon-substituted or unsubstituted aminocarbonylamino group, [for example, carbamoylamino group] , N, N-Dime Le aminocarbonylamino group, N, N-diethylamino carbonyl amino group, a morpholinocarbonylamino group]], and the like.

The monovalent organic group represented by Q _{1 to} Q ₆ can be represented in the above-described range, but is preferably an aryl group or a heteroaryl group which may have a substituent? Or the adjacent groups form a cyclic structure. More preferably, the cyclic structure comprises an optionally substituted aryl group or heteroaryl group.
As an example of the ring bond or condensed ring form, the following structures (however, description of monovalent or polyvalent bonds in the structure is omitted) can be given.

Specific examples of the aryl group or heteroaryl group which may have a substituent forming the cyclic structure include a benzene ring, a thiophene ring, a pyridine ring, a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine. A ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a furan ring, a thiophene ring, a selenophene ring, and a silole ring are preferable, and the following (i) and (ii) are more preferable.
(I): one or more of the aryl group and heteroaryl group, or a compound residue in which the rings are condensed (ii): a compound residue in which the rings in (i) are linked via a covalent bond

In addition, a π-conjugated compound selected from a combination selected from at least one group selected from the above (i) and (ii) is preferable, and each of these aromatic hydrocarbon rings or aromatic heterocycles has It is preferable that the π electron has a structure delocalized in the condensed ring or the entire linking ring by the interaction by the connection via the condensed ring and the covalent bond.
Examples of the covalent bond here include a carbon-carbon single bond, a carbon-carbon double bond, a carbon-carbon triple bond, an oxyether bond, a thioether bond, an amide bond, and an ester bond. , Either a double bond or a triple bond.

The number of aromatic hydrocarbon rings or aromatic heterocycles linked by a condensed ring or a covalent bond is preferably 2 or more. Specific examples (general formulas are given for some examples) include naphthalene, anthracene, tetracene, chrysene, pyrene [the following general formula (Ar3)], pentacene, thienothiophene [the following general formula (Ar1)], thieno Dithiophene, triphenylene, hexabenzocoronene, benzothiophene [following general formula (Ar2)], benzodithiophene, [1] benzothieno [3,2-b] [1] benzothiophene [B _n TB _n T; (Ar4)], dinaphtho [2,3-b: 2 ′, 3′-f] [3,2-b] thienothiophene [DNTT], benzodithienothiophene [TTPTT; the following general formula (Ar5)], naphtho Condensed polycyclic compounds such as dithienothiophene [TTNTTT; the following general formulas (Ar6), (Ar7)], biphenyl, terphenyl, Over terphenyl, bithiophene, terthiophene, aromatic oligomeric hydrocarbon ring and an aromatic hetero ring, phthalocyanines such as quaterthiophene, porphyrins, and the like.

In addition, the number of the soluble substituents of the present invention that are bonded or condensed to a certain main skeleton via a covalent bond naturally depends on the number of atoms that can be substituted or condensed on Ar. . For example, an unsubstituted benzene ring can be bonded via a covalent bond at a maximum of 6 substitution positions, and can be condensed at a maximum of 6 positions. However, in consideration of the molecular size of the main skeleton itself, the number of substitutions depending on the solubility, the symmetry of the molecule, and the ease of synthesis, the lower limit of the soluble substituent of the present invention contained in one molecule is 2 or more. Is more preferable. On the other hand, if the number of substitutions is too large, the soluble substituents are sterically crowded, which is not preferable. Therefore, the upper limit is a sufficient number of substitutions depending on the symmetry of the molecule, ease of synthesis, and solubility. Considering 4 or less is preferable.
The following compound precursor group is exemplified as a specific structure of the π electron conjugated compound precursor partially having a cyclohexene structure used in the present invention, but the π electron conjugated compound precursor in the present invention is limited to these. It is not something. Moreover, it can be easily inferred that the solvent-soluble substituent has a plurality of stereoisomers of the leaving substituent, and the following compound precursors include a mixture of isomers having different steric configurations.

By applying energy such as heat to the π-electron conjugated compound precursor (applying or applying an external stimulus), a desorption reaction described later is caused, and the substituents X _n and Y _n are eliminated, whereby the specific compound Can be obtained.
Examples of specific compounds obtained from the π-electron conjugated compound precursors shown in the specific examples are shown in the following specific compounds 1 to 29, but the specific compounds in the present invention are not limited to these.

[Method of producing π-electron conjugated compound by elimination reaction of π-electron conjugated compound precursor]
The method for producing a π-electron conjugated compound by the elimination reaction of the π-electron conjugated compound precursor used in the present invention will be described in detail.
In the case of the production method used in the present invention, a solution containing a plurality of π-electron conjugated compound precursors A- (B _n ) m on a substrate (support) such as plastics, metal, silicon wafer, glass, etc. A precursor-containing film is formed by coating. The external stimulus to the precursor-containing film, the elimination component represented by X _n -Y _n desorbed, converts to a compound A- (C) m having an olefinic structure. In this conversion process, a difference occurs in the time at which each elimination reaction occurs due to the difference in the likelihood of the elimination reaction of a plurality of π-electron conjugated compound precursors A- (B _n ) m.
Here, a π-electron conjugated compound precursor that undergoes a desorption reaction by a low external stimulus (for example, thermal energy) is A- (B ₁ ) m, and a higher external stimulus (for example, thermal energy) than A- (B ₁ ) m. Assuming that A- (B ₂ ) m is a π-electron conjugated compound precursor that undergoes an elimination reaction, the elimination reaction occurred first when the same external stimulus (for example, applying thermal energy) was given to them. The π-electron conjugated compound precursor A- (B ₁ ) m is converted into a π-electron conjugated compound A- (C) m, which forms a seed crystal. The π-electron conjugated compound A- (C) m converted from the π-electron conjugated compound precursor A- (B ₂ ) m that undergoes a desorption reaction thereafter undergoes crystallization following the previous seed crystal. A crystal film depending on the crystal can be formed.
The π-electron conjugated compound precursor A- (B _n ) m has different reaction temperatures and elimination reaction energies because the elimination components X _n -Y _n have different elimination components. On the other hand, this is achieved by using essential features such as producing the same A- (C) m obtained as a result of the reaction.
That is, the π-electron conjugated compound precursor A- (B _n ) m has different nucleation rates and crystal growth rates, and it is difficult to mix them to use a single precursor. It becomes possible to control the nucleus generation rate and crystal growth rate that are indispensable for high-quality crystal film formation.
In the case of the production method used in the present invention, a π-electron conjugated compound precursor A contained in a precursor-containing film formed, for example, by coating on a substrate (support) such as plastics, metal, silicon wafer, or glass. - _(B n) m _is the elimination component represented by X n -Y _n desorbed, converts to a compound A- (C) m having an olefinic structure.

π electron conjugated compound precursor A- _(B n) from m is a leaving radicals _X n, _{Y n} are defined as leaving _group, X n -Y _n are defined as desorption component. The desorbing component can take the three states of solid, liquid, and gas, but considering the removal to the outside of the system, the desorbing component is preferably liquid or gas, particularly preferably at room temperature or It becomes a gas at the temperature at which the elimination reaction is performed.
The boiling point is preferably 500 ° C. or lower at atmospheric pressure (1013 hPa), and is 400 ° C. or lower in view of the ease of removal out of the system and the decomposition / sublimation temperature of the π-electron conjugated compound produced. More preferably, it is 300 degrees C or less especially preferably.
The following X _n is an acyloxy group, Y _n is hydrogen, are shown below as an example when R ₆ is a substituted or unsubstituted alkyl group, Production Examples of the present invention is not necessarily limited thereto .

In the case of the above example, by applying external energy, the elimination reaction represented by the general formula (XI) proceeds. The carboxylic acid having an alkyl chain is eliminated and converted to a structure containing an olefin structure. When the heating temperature exceeds the boiling point of the carboxylic acid, the carboxylic acid becomes a gas.
An outline of the mechanism by which the desorbing component is desorbed from the compound represented by the general formula (XI) is shown below.

  As shown in the general formula (XII), by taking a six-membered cyclic transition state, the hydrogen atom on the β-carbon undergoes 1,5-rearrangement onto the oxygen atom of the carbonyl, resulting in concerted elimination. Reaction occurs, carboxylic acid is eliminated, and it is converted into an olefin structure as shown in the general formula (XI).

  Here, the hydrogen atoms on the β carbon can be extracted not only by oxygen atoms, but also by chalcogen atoms such as selenium, tellurium, polonium and the like which are also elements of Group 16.

Further, when m> 2, R ₁ to R ₃ can form a ring. A preferred example of forming a ring is a structure partially having a cyclohexadiene structure, and the elimination reaction will be described in detail.

The π-electron conjugated compound precursor represented by the general formula (A) of the present invention is represented by X _n -Y _n with a compound (specific compound) represented by the general formula (B _n ) by energy application. Into a compound (leaving component).

The compound represented by the general formula (XIII) has a plurality of isomers having different steric arrangements of substituents, all of which are converted into the specific compound represented by the general formula (B _n ) The separation components are the same.

The X _n and Y _n from a compound which is eliminable group represented by the general formula (A) is defined as the leaving substituent, X _n -Y _n which they are generated by combining the definition and desorption component Is done. The desorbing component can take the three states of solid, liquid, and gas, but considering the removal to the outside of the system, the desorbing component is preferably liquid or gas, particularly preferably at room temperature or It becomes a gas at the temperature at which the elimination reaction is performed.
The boiling point of the desorbing component is preferably 500 ° C. or less at atmospheric pressure (1013 hPa). Considering the ease of removal out of the system and the decomposition / sublimation temperature of the π-conjugated compound produced, the boiling point is 400 ° C. or less. More preferably, it is 300 ° C. or less.

The following is an example where X _n in the general formula (A) is an optionally substituted acyloxy group, and Y _n and Q ₁ and Q ₆ are hydrogen atoms. An expression is shown. The conversion by the detachment reaction of the π-electron conjugated compound precursor of the present invention is not limited to this.

In the case of the above example, by applying energy (heating), the carboxylic acid having the alkyl chain represented by the general formula (E) as a desorbing component is desorbed from the cyclohexadiene ring structure represented by the general formula (C). To a specific compound having a structure containing a benzene ring represented by the general formula (D).
When the heating temperature exceeds the boiling point of the carboxylic acid, the carboxylic acid quickly becomes a gas.
An outline of the mechanism by which the elimination component is eliminated from the compound represented by formula (F) is shown by the following reaction formula (scheme). The elimination mechanism of the elimination component from the cyclohexadiene ring structure used in the present invention is conversion from the following general formula (F) to the following general formula (H). In order to supplement the explanation, the elimination mechanism in the case of a cyclohexene ring [the following general formula (G)] is also shown. In the following formulae, R ₃ represents a substituted or unsubstituted alkyl group.

As shown in the above reaction formula, in the case of the cyclohexene ring represented by the general formula (F), the hydrogen atom on the β-carbon is transferred to the oxygen atom of the carbonyl by taking a six-membered transition state. By 5-rearrangement, a concerted elimination reaction occurs, the carboxylic acid compound is eliminated, and the cyclohexene ring structure is converted to a benzene ring structure represented by the general formula (H).
In the case of a compound having a cyclohexene structure having two acyloxy groups [general formula (F)], the elimination reaction is considered to proceed in two stages. First, one carboxylic acid is eliminated and the compound is represented by the general formula (G). The resulting cyclohexadiene ring structure.
At this time, the activation energy required for desorbing one molecule of carboxylic acid from the disubstituted product represented by the general formula (F) is the same as that from the one substituted product represented by the general formula (G). Since it is sufficiently larger than that required for desorption, the reaction proceeds rapidly in two stages, and is converted to a structure represented by the general formula (H).
Here, even when there are a plurality of stereoisomers due to the difference in the positional relationship between the substituents (acyloxy group and hydrogen, etc.), the above reaction proceeds although the reaction rate is different.

  The lowering of the elimination reaction of the cyclohexadiene skeleton is not limited to acyloxy groups, and similar effects can be seen with ether groups and the like.

  In the above reaction formula, the extraction and transfer of hydrogen atoms on the β carbon is the first stage of the reaction, so the reaction is considered to occur more easily as the force of attracting hydrogen atoms of oxygen atoms is stronger. The degree varies depending on, for example, the alkyl chain on the acyloxy group side, and also varies by changing the oxygen atom to a chalcogen atom such as sulfur, selenium, tellurium, polonium or the like, which is also a group 16 element.

Examples of the energy applied (applied) for carrying out this elimination reaction include heat, light, and electromagnetic waves. From the viewpoint of reactivity, yield, and post-treatment, thermal energy or light energy is desirable, especially thermal energy. Is preferred. Moreover, you may apply the said energy in presence of an acid or a base.
Usually, the elimination reaction depends on the structure of the functional group, but heating is often required from the viewpoint of reaction rate and reaction rate. The heating method for carrying out the elimination reaction includes a method of heating on a support, a method of heating in an oven, a method of irradiation with microwaves, a method of heating by converting light into heat using a laser, Although various methods, such as using a photothermal conversion layer, can be used, it is not limited to these.

The heating temperature for carrying out the elimination reaction can be in the range of room temperature (approximately 25 ° C.) to 500 ° C., and the lower limit temperature is the upper limit temperature in consideration of the thermal stability of the material and the boiling point of the elimination component. In view of energy efficiency, abundance of unconverted molecules, decomposition of the compound after conversion, sublimation, etc., a range of 40 ° C. to 500 ° C. is preferable, and thermal stability during synthesis of the π-electron conjugated compound precursor Is more preferably in the range of 60 ° C to 500 ° C, and particularly preferably in the range of 80 ° C to 400 ° C.
Regarding the heating time, the higher the temperature, the shorter the reaction time, and the lower the temperature, the longer the time required for the elimination reaction. Further, although depending on the reactivity and amount of the π-electron conjugated compound precursor, it is usually 0.5 minutes to 120 minutes, preferably 1 minute to 60 minutes, and particularly preferably 1 minute to 30 minutes.

  When light is used as an external stimulus, an infrared lamp, irradiation with light having a wavelength absorbed by the compound (for example, exposure to a wavelength of 405 nm or less), and the like may be used. At that time, a semiconductor laser may be used. For example, near-infrared laser light (usually laser light having a wavelength of around 780 nm), visible laser light (usually laser light having a wavelength in the range of 630 nm to 680 nm), and laser light having a wavelength of 390 to 440 nm can be mentioned. Laser light having a wavelength of 390 to 440 nm is particularly preferable, and semiconductor laser light having an oscillation wavelength in the range of 440 nm or less is preferably used. Among them, as a preferable light source, a blue-violet semiconductor laser light having an oscillation wavelength in the range of 390 to 440 (more preferably 390 to 415 nm) and an infrared semiconductor laser light having a central oscillation wavelength of 850 nm are half wavelength using an optical waveguide device. And blue-violet SHG laser light having a central oscillation wavelength of 425 nm.

In the elimination reaction of the detachable substituent, the acid or base acts as a catalyst, and conversion at a lower temperature is possible. Although these usage methods are not particularly limited, they may be added as they are to the π-electron conjugated compound precursor, or they may be dissolved in an arbitrary solvent and added as a solution, or they are vaporized in the atmosphere. Heat treatment may be performed in the solution, and a photoacid generator, a photobase generator, and the like may be added, and an acid and a base may be obtained in the system by light irradiation.
Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, 3,3,3-trifluoropropionic acid, formic acid, phosphoric acid, 2-butyloctanoic acid, and the like. it can.
As the photoacid generator, ionic generators such as sulfonium salts and iodonium salts and nonionic generators such as ionic photoacid generator imide sulfonate, oxime sulfonate, disulfonyldiazomethane, and nitrobenzyl sulfonate can be used. .
Examples of the base include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium hydrogen carbonate, sodium carbonate and potassium carbonate, amines such as triethylamine and pyridine, diazabicycloundecene, diazabicyclo Amidines such as nonene can be used.
As the photobase generator, carbamates, acyl oximes, ammonium salts and the like can be used.
Of these, it is preferable to carry out the reaction in an atmosphere of a volatile acid or base in view of ease of removal of the acid-base after the reaction.

  The atmosphere for the desorption reaction can be performed in the air with or without the above catalyst. However, in order to eliminate side effects such as oxidation and the influence of moisture, a system of further desorbed components is used. In order to promote the exclusion to the outside, it is desirable to carry out under an inert gas atmosphere or under reduced pressure.

  As for the method for forming an acyloxy group or the like that becomes a leaving substituent, an alcohol described later is reacted with a carboxylic acid chloride or a carboxylic acid anhydride, or by an exchange reaction between a halogen atom and a carboxylic acid silver or a carboxylic acid-quaternary ammonium salt. In addition to the method for obtaining a carboxylic acid ester, a method for obtaining a carbonate ester by reacting phosgene with an alcohol, a method for obtaining a xanthate ester by reacting an alkyl iodide after adding carbon disulfide to the alcohol, Examples include, but are not limited to, a method of obtaining amine oxide by reacting hydrogen oxide or carboxylic acid, and a method of obtaining selenoxide by reacting alcohol with orthoselenocyanonitrobenzene.

[Method of producing π-conjugated compound precursor]
The production method according to the present invention can be produced by a conventionally known method. The production method of a compound containing a detachable substituent as a core and a detachable substituent is determined by the present inventors. Patent documents disclosed (Japanese Patent Application No. 2009-209911, Japanese Patent Application Laid-Open No. 2009-275032, Japanese Patent Application No. 2010-136363, Japanese Patent Application No. 2010-162750, Japanese Patent Application No. 2010-163865) ) And its production method can be used.

  EXAMPLES Hereinafter, the present invention will be described in more detail and specifically with reference to examples. However, these examples are intended to facilitate understanding of the present invention and are not intended to limit the present invention. In each example, “part” represents “part by mass” unless otherwise specified. First, a part of a specific method for producing the π-electron conjugated compound precursor used in the present invention is shown.

  The compound is identified by NMR spectrum [JNM-ECXL (trade name) 500 MHz, manufactured by JEOL Ltd.], mass spectrometry [GC-MS, GCMS-QP2010 Plus (trade name), manufactured by Shimadzu Corporation], accurate mass analysis [LC-TofMS]. , Alliance-LCT Premier (trade name, manufactured by Waters), elemental analysis [(CHN) (CHN recorder MT-2, manufactured by Yanagimoto Seisakusho), elemental analysis (sulfur) (ion chromatography; anion analysis system: DXL320 (product) Name), manufactured by Dionex].

[Synthesis Example 1: Synthesis of Exemplified Compound Precursor 4]
Exemplified Compound 4 was synthesized by the following synthesis route.

In a 100 ml flask, Advanced Materials, 2009 21213-216. After adding 0.500 g (1.653 mmol) of dithienobenzodithiophene synthesized by the method described above and replacing with argon, 30 ml of THF was added. Then cooled to -20 ° C., was added dropwise _{n-B n u n} i of hexane solution (4.133mmol) and stirred for 1 hour.
Furthermore, after cooling to -78 ° C., 2.5 ml of DMF was added and stirred for 30 minutes, diluted hydrochloric acid was added, and the temperature was returned to room temperature. The precipitated solid was collected by filtration and washed with water, methanol, and ethyl acetate. It dried under reduced pressure and obtained 0.392g of dialdehyde bodies. (Yield 66%)
Next, 0.100 g (0.279 mmol) of the above dialdehyde was placed in a 25 ml flask and purged with argon, and then 2 ml of THF was added and cooled to 0 ° C. To this solution, 0.56 ml (1.116 mmol) of a 2.0 M THF solution of benzylmagnesium chloride was added dropwise, and the mixture was returned to room temperature and stirred for 4 hours.
Next, a saturated aqueous sodium chloride solution was added, THF was added, and the organic layer was washed with saturated brine. Next, after the solvent was distilled off under reduced pressure, the residue containing the diol was used as it was in the next reaction.
Into a 100 ml flask was charged the above residue and 3.4 mg (0.028 mmol) of N, N-dimethylaminopyridine, and after replacing with argon, 2 ml of pyridine and 0.136 ml (1.116 mmol) of pivaloyl chloride were added at room temperature. Stir for 2 days.
Next, THF was added, and the solution was washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution in this order. Subsequently, after distilling off the solvent under reduced pressure, the residue was purified by column chromatography to obtain 0.174 g of the objective exemplified compound precursor 4 as colorless crystals.
The obtained exemplary compound precursor 4 was easily dissolved in a solvent such as THF, toluene, chloroform, xylene, diethyl ether, and dichloromethane. Identification data of the exemplified compound precursor 4 are shown below.
¹ H NMR (CDCl ₃ , TMS) δ / ppm: 1.14 (18H, s), 3.25 to 3.38 (4H, m), 6.26 to 6.31 (2H, m), 7. 17 (2H, s), 7.2-7.3 (10H, m), 8.23 (2H, s).
IR (KB _n r) ν / cm ⁻¹ : 1717 (νC═O)

[Synthesis Example 2: Synthesis of 1Y Exemplified Compound Precursor 1]

  A 100 ml flask is charged with diol (2.790 mmol) and 34 mg (0.279 mmol) of N, N-dimethylaminopyridine, and after purging with argon, 20 ml of pyridine and 1.56 ml (11.16 mmol) of hexanoyl chloride are added. And stirred at room temperature overnight. Toluene was then added, washed with a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by recycle preparative GPC (manufactured by Japan Analytical Industrial Co., Ltd.) to obtain 0.44 g of Exemplified Compound Precursor 1 as colorless crystals. The obtained exemplary compound precursor 1 was easily dissolved in a solvent such as THF, toluene, chloroform, xylene, diethyl ether, or dichloromethane.

(Thermal Analysis of Exemplary Compound Precursor 1)
TG-DTA measurement (SII company make: TG / DTA200) of the exemplary compound precursor 1 was performed.
When the temperature was raised at a rate of 5 ° C./min, a weight reduction corresponding to two molecules of hexanoic acid (theoretical reduction amount 31.5%, actual reduction amount 31.4%) was observed at 150 to 240 ° C. Further, when the temperature was further increased, an endothermic peak was observed at 362 ° C. This coincided with the melting point of the specific compound 3 described in Japanese Patent Application No. 2009-171441.

[Synthesis Example 3: Synthesis of Exemplified Compound Precursor 10]

  Exemplified compound precursor 10 was synthesized by the same method as Exemplified compound precursor 1 except that amyl chloroformate was used instead of hexanoyl chloride. The obtained exemplary compound precursor 10 was easily dissolved in a solvent such as THF, toluene, chloroform, xylene, diethyl ether, or dichloromethane.

(Thermal Analysis of Exemplary Compound Precursor 10)
TG-DTA measurement of the exemplified compound precursor 10 was performed.
When the temperature was raised at a rate of 5 ° C./min, the weight decreased due to the elimination of the carbonic ester site at 150 to 190 ° C. (corresponding to 2 molecules each of pentanol and carbon dioxide, the theoretical decrease was 34.3%, measured A reduction of 33.3%) was observed. Further, when the temperature was further raised, an endothermic peak was observed at 360.3 ° C. This coincided with the melting point of the specific compound 3 described in Japanese Patent Application No. 2009-171441.

[Synthesis Example 4: Synthesis of Exemplified Compound Precursor 11]

In a 50 ml flask, 1.1 g (3.30 mmol) of 2-methyl-6-nitrobenzoic acid and 67 mg (0.55 mmol) of N, N-dimethylaminopyridine were placed and substituted with argon gas. .84 ml (6.05 mmol), 15 ml of THF and 0.291 ml (3.3 mmol) of 3,3,3-trifluoropropionic acid were added and stirred at room temperature for 30 minutes. Next, a solution in which 600 mg (1.1 mmol) of the diol was dissolved in 20 ml of THF was added, and the mixture was further stirred at room temperature for 24 hours. Next, a saturated aqueous ammonium chloride solution was added to the reaction solution, and extraction was performed 4 times with ethyl acetate.
The extracts were combined four times, washed twice with a saturated aqueous sodium hydrogen carbonate solution (50 m _n ), twice with a saturated saline solution (50 ml), and dried over sodium sulfate. The solvent was then distilled off under reduced pressure to obtain a brown oil (yield 1.2 g) as a crude product.
This was subjected to column purification [stationary phase: basic alumina (activity II), eluent: toluene] to obtain a yellow solid (yield 350 mg). Subsequently, the product was purified by recycle preparative HPLC (LC-9104, manufactured by Nippon Analytical Industries, Ltd., eluent: THF) to obtain yellow crystals (100 mg).
Finally, this crystal was recrystallized from THF / MeOH to obtain 60 mg of the target compound precursor 11 as a light yellow crystal in a yield of 60 mg.
When the purity of this crystal was measured by _n C / MS (peak area method), it was confirmed to be 99.9 mol% or more. Identification data of the exemplified compound precursor 11 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS) δ / ppm: 3.16 (q, 4H, J = 10.3 Hz), 3.31 (dd, 2H, J ₁ = 7.5 Hz, J ₂ = 6. 3 Hz), 3.40 (dd, 2H, J ₁ = 6.3 Hz, J ₂ = 8.0 Hz), 6.38 (t, 2H, J = 7.5 Hz), 5.93 (t, 1H, J = 5.2 Hz), 7.21 to 7.25 (8H), 7.28 to 7.31 (4H), 8.25 (s, 2H)

[Synthesis Example 5: Synthesis of Exemplified Compound Precursor 86]

  In a 100 ml flask, 0.500 g of the diol was placed, and the system was purged with argon. 20 ml of DMF and 20 ml of THF were added and cooled to 0 ° C. 17 mg of sodium hydride (55% paraffin dispersion) N, N-dimethylaminopyridine and 0.44 ml of acetic anhydride were added, and 0.23 g of room temperature was added little by little, followed by stirring at room temperature for 0.5 hour. To this solution was added dropwise 0.32 ml of iodomethane, and the mixture was further stirred at room temperature for 5 hours. Water was added to the reaction solution, followed by extraction with toluene. After the solution was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. Purification by recycle preparative GPC gave Exemplified Compound Precursor 86 as colorless crystals. The obtained exemplary compound precursor 86 was dissolved in a solvent such as THF, toluene, chloroform, xylene, diethyl ether, or dichloromethane.

(Thermal Analysis of Exemplary Compound Precursor 86)
TG-DTA measurement of the exemplified compound precursor 86 was performed.
When the temperature was raised at a rate of 5 ° C./min, a weight reduction corresponding to two molecules of methanol (theoretical reduction amount 11.2%, the actual reduction amount 13.9%) was observed at 170 to 320 ° C., and the specific compound Converted to 3.

[Synthesis Example 6: Synthesis of Exemplified Compound Precursor 30]

A 100 _mn round bottom flask was charged with iodine (973 mg, 2.0 mmol), ditritimethyltin (466 mg, 1 mmol), DMF (10 _mn ), bubbled with argon gas for 30 minutes, and tris (dibenzylidene). Acetone) dipalladium (0) (18.3 mg, 0.02 mmol) and tri (orthotolyl) phosphine (24.4 mg, 0.08 mmol) were added, and the mixture was stirred at room temperature for 20 hours under an argon atmosphere. The reaction solution was diluted with chloroform, insoluble material was removed by Celite filtration, water was added, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed with a saturated aqueous potassium fluoride solution, followed by saturated brine, and dried over magnesium sulfate. The filtrate was concentrated to give a red liquid. By purifying this with column chromatography (fixed layer: (neutral silica gel (manufactured by Kanto Chemical) + 10 wt% potassium fluoride, solvent: hexane / ethyl acetate, 9/1 → 8/2, v / v), A yellow solid was obtained, which was recrystallized from hexane / ethanol to obtain Exemplified Compound Precursor 30 as a yellow solid (yield 680 mg, yield 79.3%).
The analysis result of the exemplary compound precursor 30 is shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.87-0.89 (m, 12H), 1.28-1.33 (m, 16H), 1.61-1.69 (m , 8H), 1.96-2.01 (m, 4H), 2.28-2.36 (m, 12H), 6.08 (d, 4H, J = 12.1 Hz), 7.37 (d , 2H, J = 8.6 Hz), 7.48 (s, 2H), 7.57-7.59 (m, 4H)
Elemental analysis _{(C 50 H 64 O 8 S} 2): C, 69.92; H, 7.67; O, 14.85; S, 7.44 ( Found), C, 70.06; H, 7 .53; O, 14.93; S, 7.48 (theoretical value)
Melting point: 113.7-114.7 ° C
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the exemplified compound precursor 30.

[Synthesis Examples 7 and 8: Synthesis of Exemplified Compound Precursors 57 and 58]

A 100 _mn round bottom flask was charged with iodine (550 mg, 1.49 mmol), trimethyltin (346 mg, 0.74 mmol), N, N-dimethylformamide (hereinafter abbreviated as DMF, 10 m _n ), argon After bubbling gas for 30 minutes, tris (dibenzylideneacetone) dipalladium (0) (18.3 mg, 0.02 mmol), the filtrate was passed through a silica gel pad (thickness 3 cm) and then concentrated to give a red solid. This was washed with methanol and hexane to obtain a yellowish green solid (yield 235 mg).
Example compound precursor 57 and precursor 58 were obtained as yellow crystals by separating and purifying using recycle preparative HP _n C (manufactured by Nippon Analytical Industrial Co., Ltd., _n C-9104) [compound precursor 57: yield 85 mg. Compound precursor 58: yield 110 mg].

The analysis result of the compound precursor 57 is shown below.
[Compound precursor 57];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 6H, J = 6.9 Hz), 1.21-1.31 (m, 8H), 1.57-1.63 _{(m, 4H), 2.27 (} td, 2H, J 1 = 7.6Hz J 2 = 1.7Hz), 2.60-2.70 (m, 4H), 5.95 (t, 1H, J = 5.2 Hz), 6.03-6.09 (m, 4H), 6.63 (d, 2H, J = 9.7 Hz), 7.40 (d, 4H, J = 8.1 Hz), 7 .49 (s, 2H), 7.491 (dd, 2H, J ₁ = 7.7 Hz, J ₂ = 2.3 Hz)
Accurate mass ( _nC -TofMS) (m / z): 624.232 (actual value), 624.237 (calculated value)

The analysis results of the compound precursor 58 are shown below.
[Compound precursor 58];
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.86 (t, 3H, J = 7.5 Hz), 1.22-1.32 (m, 4H), 1.57-1.64 (M, 2H), 2.28 (td, 2H, J ₁ = 7.7 Hz J ₂ = 1.2 Hz), 2.62-2.72 (m, 2H), 6.03-6.10 (m , 2H), 6.63 (d, 1H, J = 9.8 Hz), 7.40-7.42 (m, 2H,), 7.46-7.52 (m, 3H), 7.53 ( s, 1H), 7.61 (s, 1H), 7.79 (dd, 2H, J ₁ = 8.6 Hz J ₂ = 1.7 Hz), 7.84 (d, 1H, J = 8.1 Hz) , 7.88 (d, 2H, J = 8.1 Hz), 8.07 (d, 1H, J = 8.1 Hz),
Accurate mass ( _nC -TofMS) (m / z): 508.149 (actual value), 508.153 (calculated value)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structures of the compound precursor 57 and the precursor 58.

[Synthesis Example 9: Synthesis of Exemplified Compound Precursor 87]
Exemplified compound precursor 87 was synthesized according to the following reaction formula (scheme).

A 100- _mn round bottom flask was charged with a diethynyl compound (275 mg, 0.785 mmol), an iodo compound (750 mg, 1.65 mmol), and copper iodide (20.0 mg), THF (30 m _n ), diisopropylethylamine (1.5 m _n ) was added and replaced with argon gas, PdCl ₂ (PPh ₃ ) ₂ (16.6 mg) was added, and the mixture was stirred at room temperature for 72 hours.
Dichloromethane (100 m _n ) and water (100 m _n ) were added to separate the organic layer, and the aqueous layer was extracted twice with dichloromethane. The combined organic layers were washed with water and then with saturated brine and dried over sodium sulfate. The filtrate was concentrated and dissolved in a minimum amount of dichloromethane and the solution was passed through an alumina pad (activity II (water content 3%)) and concentrated again to give a yellow oil. This was purified by recycled GPC (manufactured by Nippon Analytical Industrial Co., Ltd.) to obtain an exemplified compound precursor 87 as a yellow solid. (Yield 273 mg, Yield 34.7%)

The analysis results of the exemplified compound precursor 87 are shown below.
¹ H NMR (500 MHz, CDCl ₃ , TMS, δ): 0.74-0.83 (m, 12H), 1.10-1.32 (m, 24H), 1.36-1.43 (m , 4H), 1.50-1.60 (m, 4H), 2.2-2.32 (m, 2H), 2.56-2.62 (m, 2H), 2.65-2.71 (M, 2H), 6.03-6.08 (m, 4H), 6.56 (d, 2H, J = 9.0 Hz), 7.33 (s, 2H), 7.36-7.41 (M, 4H), 7.48 (s, 2H), 8.28 (s, 2H)
Accurate mass ( _nC -TofMS) (m / z): 714.336 (actual value), 714.340 (calculated value)
Mass spectrometry: GC-MS m / z = 1003 (M +), 603 (thermal decomposition product)
From the above analysis results, it was confirmed that the synthesized product was consistent with the structure of the exemplified compound precursor 87.

[Conversion film from π-electron conjugated compound precursor]
Furthermore, as a concise disclosure for facilitating understanding of the π-electron conjugated compound precursor used in the present invention and the π-electron conjugated compound obtained from the precursor, the core precursor A- (B _n ) Details of the conversion to the target compound A- (C) m by elimination of the leaving group from m will be described in detail by way of specific examples.

The hot which set (pi) electron conjugated compound precursor (1) (5 mg) shown by general formula to arbitrary temperature (150,160,170,180,220,230,240,260 degreeC) through a silicon wafer. Each sample was prepared by heating for 30 minutes on the plate.
The sample and π electron conjugated system before heating compound precursor (1), and another route π electron conjugated compound synthesized and purified in the IR spectrum (KB _n r method (2), Spectrum GX _n (trade name), Perkin Elmer). The result is shown in FIG.
Under the heating condition of Exemplified Compound 30 at 240 ° C., the absorption of —O— (1156 cm ⁻¹ and C═O (1726 cm ⁻¹⁾ ) disappears, and new absorption (810, 738, 478 cm ⁻¹ , aromatic) Existence was confirmed. This coincides with the spectrum of the π electron conjugated compound (2).
In addition, the thermal decomposition behavior of the π-electron conjugated compound precursor (1) was measured using TG-DTA (reference Al ₂ O ₃ , under a nitrogen stream (200 m _n / min), EX _n STAR6000 (trade name), Seiko Instruments Inc. The temperature was raised from 25 ° C. to 500 ° C. at a rate of 5 ° C./min. The result is shown in FIG.
In TG-DTA, a weight loss of 56.7% was observed from 160 to 290 ° C. This is almost consistent with 4 molecules of caproic acid (theoretical value: 54.2%). The presence of a melting point was observed at 357.7 ° C. This agrees with the value of the π electron conjugated compound (2).
From the above results, it was shown that the π-electron conjugated compound precursor (1) is converted to the π-electron conjugated compound (2) by heating.
It was also shown that the threshold for elimination reaction is around 240 ° C.

Using a silicon wafer (N-doped) with a thermal oxide film with a thickness of 300 nm as a substrate, cleaning the surface of the oxide film with oxygen plasma, and then spin-coating an N-methylpyrrolidone solution of polyimide resin to a thickness of about 500 nm A polyimide film was formed.
Thereafter, a π electron conjugated compound precursor film having a thickness of about 100 nm was obtained by spin coating a chloroform solution ink (1 wt%) of the π electron conjugated compound precursor (4). Thereafter, heating is performed at 230 ° C. for 5 minutes in an inert atmosphere to give external energy to convert the π-electron conjugated compound precursor (4) into the π-electron conjugated compound (5) and the elimination component (6). The obtained film was obtained.

Here, the microscope observation photograph of the single crystal of the π-electron conjugated compound (5) is shown in FIG. Furthermore, the SEM photograph of the organic film containing the (pi) electron conjugated compound (5) which is a conversion film of the (pi) electron conjugated compound precursor (4) manufactured by the said manufacturing method in FIG. 4 is shown. For comparison, an SEM photograph of a vacuum-deposited film of π-electron conjugated compound (5) is shown as another method for producing an organic film.
It is clear from out-of-plane / in-plane _Xn- ray diffraction that the thin films of FIGS. 4 and 5 have matching diffraction peaks (not shown). Therefore, it is clear that the conversion film is a film mainly containing the π electron conjugated compound (5).
As shown in FIG. 3, a single crystal of a π-electron conjugated compound obtained by solution growth or vapor phase growth shows a crystal habit in the production method. For example, the π-electron conjugated compound (5) is a plate-like crystal and has an angle of θ1 = about 130 degrees. The angle can be estimated from the crystal lattice of the π-electron conjugated compound (5).

  In the conversion film from the π-electron conjugated compound precursor used in the present invention in FIG. 4, domains in the same direction are formed, and cracks or crystal habits due to precursor conversion are visible. It has an angle of θ2 = about 130 degrees, which means that it is a conversion film from the π-electron conjugated compound precursor used in the present invention. It is clear that the vacuum-deposited film of the π-electron conjugated compound (5) shown in FIG. 5 is different, and there is a difference in the size of the domain, the shape of the domain, and the angle formed by the domain. Moreover, the organic film manufactured by this invention has a different characteristic (for example, transistor characteristic) from a vacuum evaporation film.

  As described above, the organic film converted from the π-electron conjugated compound precursor used in the present invention into the π-electron conjugated compound may be different from a film manufactured by another method such as vacuum deposition. Whether or not it is a conversion film can be easily determined from the shape and various analysis methods. Although an organic film converted from a single π-electron conjugated compound precursor to a π-electron conjugated compound has been described, from a plurality of π-electron conjugated compound precursors used in the present invention, a single π electron Whether an organic film is converted to a conjugated compound or not can also be determined.

[Electronic device]
The specific compound used in the present invention can be used, for example, in an electronic device. An example of an electronic device is a device that has two or more electrodes, the current flowing between the electrodes and the voltage generated are controlled by electricity, light, magnetism, chemical substances, etc., or the applied voltage or current Thus, a device that generates light, an electric field, or a magnetic field can be used. In addition, for example, an element that controls current or voltage by application of voltage or current, an element that controls voltage or current by application of a magnetic field, an element that controls voltage or current by the action of a chemical substance, or the like can be given. Examples of this control include rectification, switching, amplification, and oscillation.
Corresponding devices currently implemented with inorganic semiconductors such as silicon include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, etc., or these elements Combinations and integrated devices. In addition, a solar cell that generates an electromotive force by light, or an optical element such as a photodiode or a phototransistor that generates a photocurrent can be used.

  A field effect transistor (FET) is mentioned as an example of an electronic device suitable for applying the specific compound used by this invention. Hereinafter, this FET will be described in detail.

"Transistor structure"
3A to 3D are schematic structures of the organic thin film transistor according to the present invention. The organic semiconductor layer (1) of the organic thin film transistor according to the present invention contains the specific compound of the present invention. In the organic thin film transistor of the present invention, a gate electrode (4) is provided on a spatially separated source electrode (2), drain electrode (3) and a support (substrate) (not shown). ) And an organic semiconductor layer (1), an insulating film (5) may be provided. In the organic thin film transistor, the current flowing in the organic semiconductor layer (1) between the source electrode (2) and the drain electrode (3) is controlled by applying a voltage to the gate electrode (4).

The organic thin film transistor manufactured by the present invention can be provided on a support, and for example, a commonly used substrate such as glass, silicon, or plastic can be used. In addition, by using a conductive substrate, it can also be used as a gate electrode, and a structure in which a gate electrode and a conductive substrate are stacked can be used. However, the flexibility of a device to which the organic thin film transistor of the present invention is applied. When characteristics such as light weight, low cost, and impact resistance are desired, a plastic sheet is preferably used as the support.
Examples of the plastic sheet include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Is mentioned.

“Film Formation Method: Organic Semiconductor Layer”
The organic semiconductor material according to the present invention can be formed by vapor deposition such as vacuum deposition.
In addition, for example, a thin film can be formed by dissolving in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, chlorobenzene, dichlorobenzene, and xylene and coating on a support. That is, the solvent for the coating liquid containing the precursor A- (B _n ) m can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is 500 ° C. or less. It is preferable. However, the higher the volatility, the better. Those having a boiling point of 50 ° C. or higher are preferred. Although not fully confirmed, it may be because conductivity is not only the detachment of the leaving group of the precursor, but also the change of the arrangement state for contact between molecules. In other words, the precursor present in the coating film is removed from the random state and then adjoined, contacted, or regenerated between the molecules by at least a partial change in the direction or position of the molecule from the random state. This may be because it takes time for the arrangement, aggregation, crystallization, and the like to occur.
In any case, as the solvent, specifically, an alcohol such as methanol, ethanol, isopropanol or the like having an affinity for a polar carboester group as a leaving group, for example, which the precursor A- (B _n ) m has, Glycols such as ethylene glycol, diethylene glycol, propylene glycol, ethers such as tetrahydrofuran (THF), dioxane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, phenols such as phenol and cresol, dimethylformamide (DMF), pyridine, dimethylamine, In addition to nitrogen-containing organic solvents such as triethylamine, polar (water-miscible) solvents such as cellosolve (registered trademark) such as methyl cellosolve and ethyl cellosolve, toluene, xylene and benzene that have a relatively strong affinity with the main body structure Hydrocarbon hydrocarbons such as carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, etc. Examples thereof include ester solvents, nitrogen-containing organic solvents such as nitromethane and nitroethane.
These may be used alone or in combination of two or more.

Among them, polar (water-miscible) solvents such as tetrahydrofuran (THF) and halogenated hydrocarbons such as toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride, and ester systems such as ethyl acetate A combination with a non-water miscible solvent such as a solvent is particularly preferred.
Although the usage-amount of an organic solvent can be suitably selected according to the objective, it is preferable that it is 200-200000 weight part with respect to 1 weight part of precursor A- ( _Bn ) m materials.
Further, the coating solution further contains a slight amount of a resin component that does not impair the achievement of the object of the present invention, a volatile or self-decomposable acid for promoting the decomposition of the carboester group, and a base material. Also good. Further, a strongly acidic solvent such as trichloroacetic acid (decomposed into chloroform and carbon dioxide by heating) and trifluoroacetic acid (volatile) is preferably used because it has an effect of expelling a carboester group which is a weak Lewis acid.
And it can form by applying energy with respect to the film | membrane which consists of an organic-semiconductor precursor, and converting into an organic-semiconductor film.
Examples of methods for producing these organic semiconductor thin films include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, ink jet, and dispensing. Depending on the material, an appropriate solvent is selected from the above-described film forming method and the above solvent.

In the organic thin film transistor of the present invention, the thickness of the organic semiconductor layer is not particularly limited, but a uniform thin film (that is, there is no gap or hole that adversely affects the carrier transport property of the organic semiconductor layer) is formed. The thickness is selected. The thickness of the organic semiconductor thin film is generally 1 μm or less, particularly preferably 5 to 200 nm.
In the organic thin film transistor of the present invention, the organic semiconductor layer formed using the above compound as a component is formed in contact with the source electrode, the drain electrode, and the insulating film.

"electrode"
The gate electrode, source electrode, and gate electrode used in the organic thin film transistor according to the present invention are not particularly limited as long as they are conductive materials. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony, lead Tantalum, indium, aluminum, zinc, magnesium, etc., and their alloys, conductive metal oxides such as indium / tin oxide, or inorganic and organic semiconductors whose conductivity has been improved by doping, such as silicon single crystals , Polysilicon, amorphous silicon, germanium, graphite, polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline, polythienylene vinylene, polyparaphenylene vinylene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, and the like.

The source electrode and the drain electrode are preferably those having low electrical resistance at the contact surface with the semiconductor layer among the above-described conductivity.
As a method for forming an electrode, a method of forming an electrode using a known photolithographic method or a lift-off method, using a conductive thin film formed by a method such as vapor deposition or sputtering using the above materials as a raw material, a metal such as aluminum or copper There is a method of etching using a resist by thermal transfer, ink jet or the like on a foil. Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from the coating film by lithography, laser ablation, or the like. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as a relief printing plate, an intaglio printing plate, a planographic printing plate or a screen printing method can also be used.
Moreover, the organic thin-film transistor of this invention can provide the extraction electrode from each electrode as needed.

"Insulating film"
Various insulating film materials can be used for the insulating film used in the organic thin film transistor according to the present invention. For example, silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconium barium titanate, lead zirconate titanate, lead lanthanum titanate, titanate Examples thereof include inorganic insulating materials such as strontium, barium titanate, barium magnesium fluoride, bismuth tantalate niobate, and yttrium trioxide.

  Further, for example, polymer compounds such as polyimide, polyvinyl alcohol, polyvinylphenol, polyester, polyethylene, polyphenylene sulfide, unsubstituted or halogen atom-substituted polyparaxylylene, polyacrylonitrile, cyanoethyl pullulan, and the like can be used.

  Further, two or more of the above insulating materials may be used in combination. The material is not particularly limited, but a material having a high dielectric constant and a low electrical conductivity is preferable.

  Examples of the method for producing the insulating film layer using the above materials include a CVD method, a plasma CVD method, a plasma polymerization method, a dry process such as a vapor deposition method, a spray coating method, a spin coating method, a dip coating method, an ink jet method, and a cast method. Examples thereof include wet processes such as coating, blade coating, and bar coating.

"Modification of organic semiconductor / insulating film interface such as HMDS"
In the organic thin film transistor of the present invention, an organic thin film may be provided between these layers for the purpose of improving the adhesion between the insulating film and the organic semiconductor layer, reducing the gate voltage, and reducing the leakage current. The organic thin film is not particularly limited as long as it does not chemically affect the organic semiconductor layer. For example, an organic molecular film or a polymer thin film can be used.
In FIG. 16, the schematic of the example of the organic thin-film transistor using the organic film obtained by this invention is shown. In the figure, symbol (1) is an organic semiconductor layer, symbol (2) is a gate insulating film, symbol (3) is a source electrode, symbol (4) is a drain electrode, symbol (5) is a gate electrode, and symbol (6) is It is a substrate.

  Examples of the organic molecular film include a coupling agent using octyltrichlorosilane, octadecyltrichlorosilane, hexamethylenedisilazane, phenyltrichlorosilane and the like as specific examples. As the polymer thin film, the above-described polymer insulating film materials can be used, and these may function as a kind of insulating film. The organic thin film may be subjected to an anisotropic treatment by rubbing or the like.

"Protective layer"
The organic transistor according to the present invention is stably driven even in the atmosphere, but is protected as necessary for protection from mechanical destruction, protection from moisture and gas, or protection for device integration. Layers can also be provided.

"Applied devices"
The organic thin film transistor according to the present invention, a liquid crystal, an organic E _n, the display image elements such electrophoresis can be used as elements for driving, these integration is possible to produce a display referred to as "electronic paper" Is possible. Further, an IC in which the organic thin film transistor of the present invention is integrated can be used as a device such as an IC tag.

[Example 1]
Examples are shown below, but the conversion film from the π-electron conjugated compound precursor is not limited thereto.

A silicon wafer (N-doped) with a thermal oxide film having a thickness of 300 nm is used as a substrate, and the surface of the oxide film is washed with oxygen plasma, and then N of polyimide resin (copolymer of compound (7) and compound (8)). -A polyimide film having a thickness of about 500 nm was formed by spin coating a methylpyrrolidone solution.
Thereafter, a chloroform solution ink (1 wt%) of the π electron conjugated compound precursor (9) and a chloroform solution ink (1 wt%) of the π electron conjugated compound precursor (11) are mixed at a weight ratio of 1: 1, and spin By coating, a π electron conjugated compound precursor film having a thickness of about 100 nm was obtained. Then, external energy is given by performing heating at 230 ° C. for 10 minutes in an inert atmosphere, and the π-electron conjugated compound (9) and the π-electron conjugated compound precursor (11) 5) and the desorbed component (10) and desorbed component (12).
Here, a microscopic observation photograph of the π-electron conjugated compound is shown in FIG. As shown in FIG. 6, a uniform film was formed on the substrate surface.

[Comparative Example 1]
A film was formed in the same manner as in Example 1 except that the chloroform solution ink (1 wt%) of the π-electron conjugated compound precursor (9) was spin-coated alone, and then heated at 230 ° C. for 10 minutes in an inert atmosphere. As a result, external energy was applied and converted from the π-electron conjugated compound precursor (9) to the π-electron conjugated compound (5) and the elimination component (10).
Here, FIG. 7 shows a microscopic observation photograph of the π-electron conjugated compound (5) on the substrate surface. As shown in FIG. 7, a uniform film is not formed on the substrate surface, and π-electron conjugated compounds (5) are scattered.

[Comparative Example 2]
A film was formed in the same manner as in Example 1 except that the chloroform solution ink (1 wt%) of the π-electron conjugated compound precursor (11) was spin-coated alone, and then heated at 230 ° C. for 10 minutes in an inert atmosphere. As a result, external energy was applied and the π-electron conjugated compound precursor (9) was converted into a π-electron conjugated compound (5) and a desorption component (12).
Here, a microscopic observation photograph of the π-electron conjugated compound (5) on the substrate surface is shown in FIG. As shown in FIG. 8, a uniform film is not formed on the surface of the substrate, and scattered π-electron conjugated compounds (5) are scattered.

[Example 2]
Source and drain electrodes are obtained by vacuum-depositing gold (back pressure: 10 ⁻⁴ Pa, deposition rate: 1 to 2 Å / s, film thickness: 50 nm) with respect to the crystal film produced in Example 1 using a shadow mask. (Channel length 50 μm, channel width 2 mm). The organic semiconductor layer and the silicon oxide film at portions different from the electrodes were scraped off, and a conductive paste (conductive paste, manufactured by Fujikura Kasei Co., Ltd.) was applied to the portions, and the solvent was dried. Using this portion, a voltage was applied to the silicon substrate as the gate electrode.
The electrical characteristics of the FET (field effect transistor) element thus obtained were evaluated in the atmosphere using a semiconductor parameter analyzer 4156C manufactured by Agilent. The results are shown in the following table.

[Comparative Example 3]
An organic semiconductor device was produced in the same manner as in Example 2 except that the crystal film produced in Comparative Example 1 was used, and electrical characteristics (mobility) were evaluated. The results are shown in the following table.

[Comparative Example 4]
An organic semiconductor device was produced in the same manner as in Example 2 except that the crystal film produced in Comparative Example 2 was used, and electrical characteristics (mobility) were evaluated. The results are shown in the following table.

[Example 3]

A silicon wafer (N-doped) with a thermal oxide film having a thickness of 300 nm is used as a substrate, the surface of the oxide film is cleaned with oxygen plasma, and then an N-methylpyrrolidone solution of polyimide resin (CT4112 manufactured by Kyocera Chemical Co.) is spin-coated Thus, a polyimide film having a thickness of about 500 nm was formed.
Thereafter, the chloroform solution ink (1 wt%) of the π electron conjugated compound precursor (4) and the chloroform solution ink (1 wt%) of the π electron conjugated compound precursor (13) are mixed at a weight ratio shown in the following table, Each adjustment liquid was spin-coated to obtain a π-electron conjugated compound precursor film having a thickness of about 100 nm. Thereafter, each π-electron conjugated compound precursor film is heated at 230 ° C. for 10 minutes in an inert atmosphere to give external energy, and the π-electron conjugated compound precursor (4) and the π-electron conjugated compound precursor The product (13) was converted into a π-electron conjugated compound (5), a leaving component (6), and a leaving component (14).
Here, FIGS. 11 to 15 show microscopic observation photographs of thin films 1 to 6 of the π-electron conjugated compound.
Further, FIG. 9 shows the result of thermal analysis (TG) of TGDTA of the π-electron conjugated compound precursor (4). A decrease in weight from 160 ° C. to 250 ° C. corresponds to an elimination reaction, and a decrease in weight at 350 ° C. or higher is due to a decomposition reaction. The weight loss associated with the elimination reaction agrees with the theoretical value estimated from the molecular weight, and it can be seen that a good elimination reaction is performed.
The result of the thermal analysis (TG) of TGDTA of the π-electron conjugated compound precursor (13) is shown in FIG. The weight reduction from 140 ° C. to 180 ° C. corresponds to the elimination reaction, and the weight reduction above 350 ° C. is due to the decomposition reaction. The weight loss associated with the elimination reaction agrees with the theoretical value estimated from the molecular weight, and it can be seen that a good elimination reaction is performed.
From the results of the thermal analysis of FIGS. 4 and 5, it can be seen that the conjugated compound precursor (13) undergoes a desorption reaction at a lower temperature.
When the above-mentioned π-electron conjugated compound precursors (4) and (13) are mixed to form a thin film, the π-electron conjugated compound precursor (13) of FIG. 9 and FIG. The elimination reaction takes place earlier and contributes as a seed crystal, and the π-electron conjugated compound precursor (4) subsequently undergoes the elimination reaction and contributes to crystal growth. Thin film 1: FIG. 11 and thin film 2: FIG. 12 has a large number of π-electron conjugated compound precursors (13) to be seed crystals, and therefore has a smaller crystal domain than other thin films. Thin film 4: The largest crystal domain is formed under the weight ratio condition of FIG. 14, and a larger domain formation is seen than under the condition of thin film 5: compound (4) alone in FIG. 15.

[Example 4]
The thin film 4 prepared in Example 3 was subjected to vacuum deposition using a shadow mask (back pressure: 10 ⁻⁴ Pa, deposition rate: 1 to 2 ｓ / s, film thickness: 50 nm), and source and drain electrodes (Channel length 50 μm, channel width 2 mm). The organic semiconductor layer and the silicon oxide film at portions different from the electrodes were scraped off, and a conductive paste (conductive paste, manufactured by Fujikura Kasei Co., Ltd.) was applied to the portions, and the solvent was dried. Using this portion, a voltage was applied to the silicon substrate as the gate electrode.
The electric characteristics of the FET (field effect transistor) element thus obtained were evaluated in the atmosphere using an Agilent semiconductor parameter analyzer 4156C. As a result, the characteristics as a p-type transistor element were shown. The results are summarized in the following table.

[Comparative Example 5]
An organic semiconductor device was produced in the same manner as in Example 4 except that the crystal film produced using the π-electron conjugated compound precursor (4) used in Examples 3 and 4 was used, and the electrical characteristics (mobility). Was evaluated. The results are shown in the following table.

[Comparative Example 6]
An organic semiconductor device was produced in the same manner as in Example 4 except that the crystal film produced using the π-electron conjugated compound precursor (13) used in Examples 3 and 4 was used, and the electrical characteristics (mobility). Was evaluated. The results are shown in the following table.

[Examples 5, 6, and 7]

A silicon wafer (N-doped) with a thermal oxide film having a thickness of 300 nm is used as a substrate, the surface of the oxide film is cleaned with oxygen plasma, and then an N-methylpyrrolidone solution of polyimide resin (CT4112 manufactured by Kyocera Chemical Co.) is spin-coated Thus, a polyimide film having a thickness of about 500 nm was formed.
Thereafter, chloroform solution inks (1 wt%) of π-electron conjugated compound precursors (58), (57), and (30) were mixed at a weight ratio shown in Table 15 to prepare an adjustment ink. Each adjustment ink was spin-coated to obtain a π-electron conjugated compound precursor film having a thickness of about 100 nm. Thereafter, each π-electron conjugated compound precursor film is heated to 180 ° C. for 10 minutes in an inert atmosphere to be converted into a π-electron conjugated compound (specific compound 17) and a desorption component elimination component (6). did.
Source and drain electrodes were formed on each thin film by vacuum deposition of gold using a shadow mask (back pressure: 10 ⁻⁴ Pa, deposition rate: 1 to 2 Å / s, film thickness: 50 nm) (channels) (Length 50 μm, channel width 2 mm). The organic semiconductor layer and the silicon oxide film at portions different from the electrodes were scraped off, and a conductive paste (conductive paste, manufactured by Fujikura Kasei Co., Ltd.) was applied to the portions, and the solvent was dried. Using this portion, a voltage was applied to the silicon substrate as the gate electrode.
The electric characteristics of the FET (field effect transistor) element thus obtained were evaluated in the atmosphere using an Agilent semiconductor parameter analyzer 4156C. As a result, the characteristics as a p-type transistor element were shown. The results are summarized in Table 15.

[Comparative Examples 7, 8, 9]
As a comparative example, Table 15 shows the results of the precursor (58), the precursor (57), and the precursor (30) alone.

1 Organic Semiconductor Layer 2 Gate Insulating Film 3 Source Electrode 4 Drain Electrode 5 Gate Electrode 6 Substrate

Japanese Patent Laid-Open No. 5-05568 WO2006-077788 JP 2007-224019 A JP 2008-270843 A JP 2009-105336 A JP 2009-188386 A JP 2009-215547 A JP 2009-239293 A JP 2009-28394 A JP 2009-84555 A JP 2009-88483 A JP 2006-352143 A JP 2009-275032 A Japanese Patent Application No. 2009-209911

Appl.Phys.lett. 72, p1854 (1998) J. Am. Chem. Soc. 128, p12604 (2006) J. Am. Chem. Soc. 129, p15732 (2007) Adv. Mater., 11, p480 (1999) J.Appl.Phys.100, p034502 (2006) Appl.Phys.lett.84,12, p2085 (2004) J. Am. Chem. Soc. 126, p1596 (2004)

Claims (7)

As shown in the following general formula (I), a coating film formed by applying a coating liquid containing at least two or more kinds of π-electron conjugated compound precursor A- (Bn) m, method of manufacturing an organic film which comprises a step of converting π electron conjugated compound A- (C) m and the leaving substituent X _n -Y _n.

(Here, A is a π-electron conjugated substituent, and B _n is a solvent-soluble substituent having at least a partial structure having the structure represented by the general formula (II). N is the solvent-soluble substituent. A natural number of 2 or more representing the type of group, m is a natural number representing the number of detachable substituents bonded to the solvent-soluble substituent, and C is at least a part of the structure represented by the general formula (III). R ₁ to R ₃ are a hydrogen atom or a substituent, and may form a ring with each other, or may form a ring with A through a covalent bond.
In the general formulas (I) and (II), one of X _n and Y _n represents a hydrogen atom and the other represents a detachable substituent. When m ≧ 2, detachable substitution of X _n or Y _n The groups may be the same as or different from each other, and may form the cyclic leaving substituent. However, _Bn is linked to any atom on A in the above general formula (I) via a covalent bond. ) The manufacturing leaving substituent X _n or Y _n is optionally substituted C 1 or more carbon also an organic film according to claim 1, characterized in that the [ether group or an acyloxy group] Method. The π-electron conjugated substituent A is
(I) one or more aromatic hydrocarbon rings and aromatic heterocycles, or a compound residue in which two or more of the rings are condensed,
And (ii) a π-electron conjugated compound residue selected from the group consisting of a compound residue in which the rings of (i) are linked via a covalent bond. The manufacturing method of the organic film of description.   The substituent A is a condensed compound residue selected from a thiophene ring and a benzene ring or a π-electron conjugated compound residue selected from a compound residue in which the rings of the compound are linked via a covalent bond The manufacturing method of the organic film in any one of Claim 1 to 3.   An organic film obtained by the production method according to claim 1.   An organic electronic device using the organic film according to claim 5.   The organic electronic device according to claim 6, wherein the organic electronic device is a field effect transistor.

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