JP6205737B2 - Manufacturing method of laminated device and laminated device - Google Patents

Description

  The present invention relates to a method for manufacturing a laminated device and a laminated device.

As a laminated device using an organic material, most of the commercialized organic EL elements (OLEDs) have a light emitting layer formed by an evaporation method. Since the vapor deposition method can be easily multi-layered, functional separation is achieved, and high efficiency and long life are achieved.
On the other hand, film formation by a coating method such as ink jet or printing is advantageous for increasing the area because of its small size dependency, but there is a problem that efficiency and life are inferior. In order to extend the lifetime of the organic EL element by the coating method, functional separation by multilayering is considered to be effective as in the vapor deposition method. When multi-layering is performed by coating, it is necessary to devise a technique that does not dissolve the groundwork.

As a method for imparting solvent resistance, introduction of a curing system is well known. For example, an oligomer or a polymer formed from a monomer including a polymerizable substituent and an electron transport unit is used. After coating this, external polymerizable energy such as heat or light is applied to cause the polymerizable substituent to react and crosslink. Thereby, the polymer obtained can be insolubilized. However, the presence of a crosslinkable substituent hinders the carrier transmission route, and the film density decreases, so that there is a problem that ions can pass through the obtained light emitting layer and is easily deteriorated. It is hard to say that it is a countermeasure.
This problem is related to an organic thin film solar cell using a conductive polymer aqueous solution (PEDOT / PSS) in which poly (3,4-ethylenedioxythiophene) (PEDOT) is doped with polystyrene sulfonic acid (PSS) as a transparent electrode. The same applies to the middle class.

  On the other hand, polyphenylene having a phenyl group linked thereto has been studied as a field effect transistor, electroluminescence, a carrier transport material to a thin film solar cell, and a conductive material. However, rigid polymers such as unmodified polyphenylene are disadvantageous in that they are insoluble in a solvent and thermally infusible, and are difficult to form and cannot be thinned.

Therefore, a number of methods for forming a film by dissolving a polymer represented by the following structural formula (a) by modifying a branched solvent-soluble substituent on the side chain of the polymer have been reported (for example, Non-Patent Document 1). However, in these methods, since the polymer has a solvent-soluble substituent, the number of sites responsible for electron transfer is relatively reduced, so that the conductive property cannot be expected, and the thin film is less stable to solvents and heat. There is a problem of lacking.

Furthermore, a method for producing polyphenylene by polymerizing after vapor deposition of a monomer has been reported (for example, Non-Patent Document 2). However, since this method requires a vacuum process, it cannot be applied to a simple wet process.
Moreover, a copolymer of an unsubstituted metaphenylene group and an unsubstituted orthophenylene is exemplified, and it is shown that the copolymer has solubility in a solvent (for example, Patent Document 1).

  Although there are many approaches to solubilization in rigid polymers such as polyphenylene, there are still materials and manufacturing methods that are highly soluble, easy to form and process, and compatible with solvent resistance after processing. Not disclosed. For example, a method for easily forming an insoluble and infusible polyphenylene polymer into a thin film is not disclosed. This hinders application development to laminated electronic devices.

  In this solution, that is, a method having both the solubility required for coating and the solvent resistance required for lamination, a π electron containing a benzene ring using a precursor that can be converted from a soluble structure to an insoluble structure. Methods for obtaining conjugated compounds have been proposed (for example, Patent Documents 2 and 3). In addition, as a method for forming a polymer, methods using a polymer precursor have been proposed (for example, Non-Patent Documents 3, 4, and 5).

In these proposals, for example, in the method represented by the following reaction formula (A), a vinylene group is generated by heating. However, in this proposal, since the desorbing components are tetrahydrothiophene and HCl, there is a possibility that they may be chemically doped, which is not preferable in terms of conductive properties, and that the olefin moiety is not thermally stable.

Furthermore, a method represented by the following reaction formula (B) has been reported.
In this method, an alkene is eliminated by introducing an ester group into polythiophene and heating it. However, in this method, a carboxylic acid residue is inevitably generated in the main chain, and there is a concern that problems may arise in the conductive properties. Furthermore, for example, it is not a fundamental solution for obtaining unsubstituted polyphenylene polymers.

On the other hand, a method using a precursor for a polyphenylene polymer has been proposed (for example, Non-Patent Documents 5 and 6).
In this proposal, for example, poly (1,4-phenylene) having an ester group in the side chain is synthesized by a coupling reaction of 2-methoxycarbonyl-1,4-dichlorobenzene, and this is hydrolyzed and decarboxylated. Thus, poly (1,4-phenylene) is obtained (see the following reaction formula (C)). However, in these proposals, only powders are obtained, and it is limited only to unsubstituted polyparaphenylene. It does not develop into other polymers, and has not made progress since it was reported. is the current situation.

  That is, in view of the above problems, a clear method for obtaining a polymer film after applying and processing a solvent-soluble polymer precursor is not disclosed, and disclosed for use in a laminated electronic device. It is hard to say that there is.

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention can form a polyphenylene polymer that is difficult to form by a coating method, and can achieve both solvent solubility before film formation and solvent resistance after film formation. An object of the present invention is to provide a method of manufacturing a laminated electronic device that can be manufactured easily.

Means for solving the problems are as follows. That is,
The method for producing a laminated electronic device of the present invention is a method for producing a laminated electronic device comprising at least one organic layer,
A coating step of coating a solution containing at least one of a polymer having a partial structure represented by the following general formula (II) and a polymer having a partial structure represented by the following general formula (III);
A moiety represented by the following general formula (I) is at least one of a polymer having a partial structure represented by the general formula (II) and a polymer having a partial structure represented by the general formula (III). An organic layer forming step of forming the organic layer containing a polymer having a partial structure represented by the general formula (I) by converting into a polymer having a structure;
It is characterized by including.
[In General Formula (I), Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring. It may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or An aryl group, m represents the number of modifications to the benzene ring forming the main chain, is an integer of 1 to 4, and when n ≧ 2, R _{1 to} R ₄ may be the same as each other If m ≧ 2, R _{1 to} R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]
[In general formulas (II) and (III), _one of X ₁ and Y ₁ is a hydrogen atom, the other is a leaving substituent, one of X ₂ and Y ₂ is a hydrogen atom, and the other is a leaving atom. One of X ₃ and Y ₃ is a hydrogen atom, and the other is a leaving substituent, and each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted group. A substituted acyloxy group, Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring; , Which may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl M is the benzene ring that forms the main chain Indicates the number of modifications, an integer from 1 to 4, provided that when n ≧ _2, or different to R 1 to R ₄ may each be identical to each other, the case of m ≧ _2, R 1 ~R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]

  According to the present invention, it is possible to solve the above-mentioned problems in the prior art, achieve the object, and form a polyphenylene polymer that is difficult to form by a coating method. It is possible to provide a method for producing a laminated electronic device that can achieve both solvent resistance after film formation and can easily produce a laminated device that is a hetero laminate.

FIG. 1 is a graph showing the results of MALDI-TOFMS measurement of Example Compound 1 (after conversion) which is an example of a polymer having a partial structure represented by the general formula (I) according to the present invention. FIG. 2 is a graph showing the results of TG-DTA and DSC measurements of the conversion process of Exemplary Compound 1 which is an example of a polymer having a partial structure represented by the general formula (I) according to the present 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.

(Manufacturing method of laminated electronic device)
The method for manufacturing a laminated electronic device of the present invention is a method for producing a laminated electronic device including at least one organic layer, and includes at least a coating step and an organic layer forming step, and further includes other steps as necessary. Including.
<Application process>
The application step is a step of applying a solution containing at least one of a polymer having a partial structure represented by the following general formula (II) and a polymer having a partial structure represented by the following general formula (III). is there.
<Organic layer formation process>
In the organic layer forming step, at least one of a polymer having a partial structure represented by the general formula (II) and a polymer having a partial structure represented by the general formula (III) is represented by the following general formula ( It is a step of forming the organic layer containing a polymer having a partial structure represented by the general formula (I) by converting to a polymer having a partial structure represented by I).
Hereinafter, the polymer having a partial structure represented by the general formulas (I) to (III) may be referred to as polymers (I) to (III), respectively.

[In General Formula (I), Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring. It may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or An aryl group, m represents the number of modifications to the benzene ring forming the main chain, is an integer of 1 to 4, and when n ≧ 2, R _{1 to} R ₄ may be the same as each other If m ≧ 2, R _{1 to} R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]
[In general formulas (II) and (III), _one of X ₁ and Y ₁ is a hydrogen atom, the other is the above-mentioned leaving group, one of X ₂ and Y ₂ is a hydrogen atom, and the other is the above-mentioned A leaving substituent, one of X ₃ and Y ₃ is a hydrogen atom, the other is the leaving substituent, and each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or A substituted or unsubstituted acyloxy group, and Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups are bonded to each other to form a ring. May be condensed with an adjacent benzene ring, n represents a repetition, and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, or an alkyl group. Or an aryl group, and m forms a main chain Indicates the number of modifications to the benzene ring, an integer from 1 to 4, provided that when n ≧ 2, or different to R ₁ to R ₄ may each be identical to each other, the case of m ≧ 2, R _{1 to} R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]

More specifically, the organic layer forming step is a partial structure represented by the general formula (II) given external energy as shown in at least one of the following reaction formula (1) and the following reaction formula (2). And a polymer having a partial structure represented by the general formula (II) by removing a detachable substituent from at least one of the polymer having a partial structure represented by the general formula (III). A polymer having a partial structure represented by the general formula (I) and a leaving compound X ₁ -Y ₁ , at least one of a polymer and a polymer having a partial structure represented by the general formula (III); It is a step of forming the organic layer containing a polymer having a partial structure represented by the general formula (I) by converting to at least one of X ₂ -Y ₂ and X ₃ -Y ₃ .

  As a result of intensive studies, the present inventors obtained an organic layer (polymerized film) that is simply insoluble or hardly soluble by applying external energy after applying and processing a polymer precursor soluble in a solvent. Thus, it was found that a hetero laminate can be produced. Furthermore, it discovered that the organic electronic device (for example, a field effect transistor, an electroluminescence, a thin film solar cell element) which is a hetero laminated body simply can be provided by the apply | coating method.

-Π electron conjugated site precursor and π electron conjugated site-
The partial structure represented by the general formula (I) includes a partial structure (i) (partial structure represented by the following general formula (i)), which is a π-electron conjugate site.
The partial structure represented by the general formula (II) and the partial structure represented by the general formula (III) are respectively a partial structure (ii) (a partial structure represented by the following general formula (ii)) and a partial structure. (Iii) (partial structure represented by the following general formula (iii)), which are π electron conjugated site precursors.

The π-electron conjugated site can be obtained by applying external energy to the π-electron conjugated compound precursor having a specific solvent-soluble substituent to desorb the detachable substituent (the following reaction formula) (3) and reaction formula (4)).
The partial structure (iii) which is the π-electron conjugated site precursor is a structure partially having a cyclohexene structure, and the partial structure (ii) is a structure partially having a cyclohexadiene structure.

In the general formulas (ii) and (iii) (the same applies to the general formulas (II) and (III)), _one of X ₁ and Y ₁ is a hydrogen atom, the other is the leaving substituent, and X ₂ And Y ₂ , one is a hydrogen atom, the other is the above-described leaving substituent, and one of X ₃ and Y ₃ is a hydrogen atom, and the other is the above-described leaving substituent.
Each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted acyloxy group.
By having the leaving substituent and the cyclohexene structure or the cyclohexadiene structure, even the rigid structure can impart solubility to the polymer (II) or the polymer (III). Film forming processability can be obtained.

--Leaving substituent--
The leaving substituent is not particularly limited as long as it is a substituted or unsubstituted alkoxy group or a substituted or unsubstituted acyloxy group, and can be appropriately selected according to the purpose.
Examples of the substituted or unsubstituted alkoxy group include substituted or unsubstituted linear or cyclic aliphatic alcohols, alkoxy groups derived from alcohols such as aromatic alcohols, and the like. A thioalkoxy group in which an oxygen atom in the alkoxy group 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 thioalkoxy groups in which oxygen is replaced with sulfur are included as well.

Examples of the substituted or unsubstituted acyloxy group include a formyloxy group, a linear or cyclic aliphatic carboxylic acid which may contain a halogen atom, an carboxylic acid such as an aromatic carboxylic acid, and an acyloxy group derived from a carbonic acid half ester. Is mentioned. Further, an acyloxy group derived from 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 group, hexanoyloxy group, lauroyloxy group, stearoyloxy group, trifluoro Acetyloxy group, 3,3,3-trifluoropropionyloxy group, pentafluoropropionyloxy group, cyclopropanoyloxy group, cyclobutanoyloxy group, cyclohexanoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy Group, pentafluorobenzoyloxy group and the like.
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 and the alkyl group or aryl group can also be mentioned. In addition, corresponding acylthiooxy groups and thioacyloxy groups in which one or more of oxygen at the ether bond site and the carbonyl site are replaced with sulfur are also included.

Some of the leaving substituents are exemplified below.
In the structural formulas exemplified below, “ ^* ” represents a bond, “Et” represents an ethyl group, and “Ph” represents a phenyl group.

Examples of the group represented by Q _{1 to} Q ₆ include a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or a monovalent organic group as described above. (However, a monovalent organic group other than the leaving substituent in Q ₁ to Q _6), and the like. Alternatively, any one of Q _{1 to} Q ₆ may be a bond, may be bonded to each other between adjacent groups to form a part of a ring, and It may be condensed.

Examples of the monovalent organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxyl group, a thioalkoxyl group, an aryloxy group, a thioaryloxy group, a heteroaryloxy group, and a heteroaryl. Examples include a ruthiooxy group, a cyano group, a hydroxyl group, 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 of the linear or branched alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecane 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 and the like can be mentioned.
Examples of the cyclic alkyl group (cycloalkyl group) include a cyclopentyl group, a cyclobutyl group, a cyclohexyl group, and a pentafluorocyclohexyl group.
In other monovalent organic groups described below, the alkyl group represents an alkyl group of the above concept.

The alkenyl group represents a linear or branched or cyclic substituted or unsubstituted alkenyl group.
Examples of the linear or branched alkenyl group include those in which any carbon-carbon single bond of the alkyl group having 2 or more carbon atoms is one or more double bonds, such as an 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, 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, 3-octenyl group, 4-octenyl group, 1,1, Examples thereof include a 1-trifluoro-2-butenyl group.
Examples of the cyclic alkenyl group (cycloalkenyl group) include those in which one or more carbon-carbon single bonds of the cycloalkyl group having 3 or more carbon atoms are double bonds [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 Group, 3-cycloheptenyl group, 4-cycloheptenyl group, 3-fluoro-1-cyclohexenyl group and the like.
In addition, 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. Good.

  Examples of the alkynyl group include those in which at least one carbon-carbon single bond of the alkyl group is one or more triple bonds. Examples of such alkynyl group include ethynyl group, propargyl group, trimethylsilylethynyl group, triisopropylsilylethynyl group and the like.

  Examples of the aryl group include phenyl, o-tolyl, m-tolyl, p-tolyl, p-chlorophenyl, p-fluorophenyl, p-trifluorophenyl, naphthyl, and the like.

  Examples of the heteroaryl group include 2-furyl, 2-thienyl, 3-thienyl, 2-thienothienyl, 2-benzothienyl, 2-pyrimidyl and the like.

  Specific examples of the alkoxyl group and thioalkoxyl group include those in which an oxygen atom or a sulfur atom is inserted into the bonding position of the alkyl group, alkenyl group, and alkynyl group exemplified above to form an alkoxy group or a thioalkoxy group. .

  Specific examples of the aryloxy group and thioaryloxy group include those in which an oxygen atom or a sulfur atom is inserted into the binding site of the aryl group exemplified above to form an aryloxy group or a thioalkoxy group.

  Specific examples of the heteroaryloxy group and heterothioaryloxy group include heteroaryloxy groups or heteroarylthioaryloxy groups formed by inserting an oxygen atom or a sulfur atom into the binding site of the heteroaryl group exemplified above. Take as an example.

Examples of the amino group include an amino group (—NH ₂ ), a substituted or unsubstituted alkylamino group (eg, methylamino group, dimethylamino group), a substituted or unsubstituted anilino group (eg, anilino group, N -Methyl-anilino group), diphenylamino group, acylamino group [for example, formylamino group, substituted or unsubstituted alkylcarbonylamino group (for example, acetylamino group, pivaloylamino group, lauroylamino group), substituted or unsubstituted aryl Carbonylamino group (for example, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group)], aminocarbonylamino group (for example, carbon-substituted or unsubstituted aminocarbonylamino group, for example, carbamoyl Amino group, N, N-dimethylaminocarbonylamino Group, N, N-diethylamino carbonyl amino group, morpholinocarbonylamino group).

The monovalent organic group represented by Q _{1 to} Q ₆ can be represented in the above-described range, and among these, an aryl group or a heteroaryl group which may have a substituent. It is preferable that adjacent or adjacent groups form a ring structure, and the ring structure is more preferably an aryl group or a heteroaryl group which may be substituted.
Examples of the ring structure (ring bond, condensed ring form) include the structures shown below. In the following structure, one of X and Y represents a hydrogen atom, and the other represents the above-mentioned leaving substituent.

[Method of generating π-electron conjugated site by conversion from π-electron conjugated site precursor]
A method for generating a π-electron conjugated site by the elimination reaction of the leaving compound from the π-electron conjugated site precursor will be described in detail.
The π-electron conjugated site precursor represented by the following general formula (A), which is a partial structure of the general formula (II), has a π-electron conjugated site represented by the following general formula (B) and X- Conversion into a leaving compound (leaving component) represented by Y (see the following reaction formula (5)).

  The π-electron conjugated site precursor represented by the general formula (A) includes a plurality of isomers having different steric arrangements of substituents, all of which have a specific structure represented by the general formula (B). The leaving compound that is converted to a π-electron conjugated site having the same is also the same.

  One of X and Y, which is a group leaving from the compound represented by the general formula (A), is a hydrogen atom, the other is the above-described leaving substituent, and XY formed by combining them is a desorption. Defined as isolated compound. The elimination compound can take three states of solid, liquid, and gas. However, considering removal to the outside of the system, the elimination compound is preferably a liquid or a gas, and is a gas at room temperature or is a desorption. More preferably, it becomes a gas at the reaction temperature.

  The boiling point of the leaving compound is preferably 500 ° C. or less at atmospheric pressure (1013 hPa). Considering the ease of removal out of the system and the decomposition or sublimation temperature of the π-conjugated compound produced, the boiling point is 400 ° C. or less. More preferably, it is particularly preferably 300 ° C. or lower.

In the following, a case where X in the general formula (A) is a substituted or unsubstituted acyloxy group and Y and Q ₁ and Q ₆ are hydrogen atoms is taken as an example, and a conversion formula by the elimination reaction (the following reaction formula) (6)). The conversion by the leaving reaction of the substituent leaving compound of the present invention is not limited to this.
In the case of the reaction formula (6), a carbox having an alkyl chain represented by the general formula (E) as a leaving compound from the cyclohexadiene ring structure represented by the general formula (C) by external energy application (heating). The acid is eliminated and converted 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.

The mechanism by which the leaving compound is eliminated from the compound represented by the general formula (F) is outlined by the following reaction formula (7) (scheme).
The elimination mechanism of the elimination compound from the cyclohexadiene ring structure 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 reaction formula (7), R ₃ represents a substituted or unsubstituted alkyl group.
As shown in the reaction formula (7), in the case of the cyclohexene ring represented by the general formula (F), the hydrogen atom on the β-carbon is moved onto the oxygen atom of the carbonyl by taking a transition state of a six-membered ring. The 1,5-rearrangement causes a concerted elimination reaction, whereby the carboxylic acid compound is eliminated and converted from a cyclohexene ring structure to a benzene ring structure represented by the general formula (H).

In the case of a partial structure [general formula (F)] having a cyclohexene structure having two acyloxy groups, it is considered that the elimination reaction proceeds in two steps. First, one carboxylic acid is eliminated and the general formula (G) The resulting cyclohexadiene ring structure is obtained.
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 a plurality of stereoisomers exist due to the difference in positional relationship between substituents (acyloxy group and hydrogen, etc.), the reaction proceeds although the reaction rate is different.

  The temperature reduction of the elimination reaction of the cyclohexadiene skeleton is not limited to the acyloxy group, and the same effect can be seen with the alkoxy group.

  In the above reaction formula, the extraction and transfer of hydrogen atoms on the β carbon is the first stage of the reaction, and therefore, the stronger the force of attracting hydrogen atoms of oxygen atoms, the more likely the reaction occurs. The degree varies depending on, for example, the alkyl chain on the acyloxy group side, and also varies by substituting oxygen atoms with chalcogen atoms such as sulfur, selenium, tellurium, and polonium, which are also elements of Group 16.

  There is no restriction | limiting in particular as external energy provided in order to perform this elimination reaction, According to the objective, it can select suitably, For example, a heat | fever, light, electromagnetic waves etc. are mentioned. Among these, from the viewpoints of reactivity, yield, and post-treatment, thermal energy and light energy are preferable, and thermal energy is more preferable. Further, the energy may be applied in the 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 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of heating on a support, a method of heating in an oven, a method using microwave irradiation, and a laser. And a method of heating by converting light into heat, a method of using a photothermal conversion layer, and the like.
The heating temperature can be in the range of room temperature (approximately 25 ° C.) to 500 ° C., and the lower limit temperature is in terms of the thermal stability of the material and the boiling point of the leaving compound. In terms of the abundance of unconverted molecules, decomposition of the compound after conversion, sublimation, etc., 40 ° C. to 500 ° C. is preferable, and 60 ° C. to 500 ° C. is more preferable in terms of thermal stability of the precursor synthesis. 80 ° C to 400 ° C is particularly preferable.
As 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 more preferably 1 minute to 30 minutes.

  In the case where light is used as external energy, 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. Examples of the light include a near-infrared laser beam (usually a laser beam having a wavelength near 780 nm), a visible laser beam (usually a laser beam having a wavelength in the range of 630 nm to 680 nm), and a laser having a wavelength of 390 to 440 nm. And semiconductor laser light having an oscillation wavelength of 440 nm or less. Among these, a laser beam having a wavelength of 390 to 440 nm, a semiconductor laser beam having an oscillation wavelength of 440 nm or less is preferable, a blue-violet semiconductor laser beam having an oscillation wavelength of 390 nm to 440 nm (more preferably 390 nm to 415 nm), and a central oscillation wavelength More preferred is a blue-violet SHG laser beam having a central oscillation wavelength of 425 nm, which is a half wavelength of an infrared semiconductor laser beam of 850 nm using an optical waveguide device.

  In the elimination reaction of the leaving substituent, the acid or base acts as a catalyst, and conversion at a lower temperature is possible. The method of using the acid or base is not particularly limited, but it may be added as it is to the substituent-eliminating compound, or it may be dissolved in an arbitrary solvent and added as a solution, and it is vaporized in the atmosphere. Heat treatment may be performed in the interior, 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. .
Examples of the photoacid generator include ionic photoacid generators such as sulfonium salts and iodonium salts; nonionic photoacid generators such as imide sulfonate, oxime sulfonate, disulfonyldiazomethane, and nitrobenzyl sulfonate. .

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 and diaza Amidines such as bicyclononene are exemplified.
Examples of the photobase generator include carbamates, acyl oximes, and ammonium salts.

It is preferable to perform the elimination reaction in a volatile acid or base atmosphere from the viewpoint of easy removal of the acid or base outside the system after the reaction.
The atmosphere for the desorption reaction can be performed in the air regardless of the presence or absence of the catalyst. However, in order to eliminate side reactions 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 preferable to carry out under an inert gas atmosphere or under reduced pressure.

  The method for forming an acyloxy group or the like, which is an example of the leaving substituent, is not particularly limited and can be appropriately selected depending on the purpose. For example, an alcohol and a carboxylic acid chloride or a carboxylic acid anhydride described below can be used. A method of obtaining a carboxylic acid ester by reacting or exchanging a halogen atom with a silver carboxylate or carboxylic acid-quaternary ammonium salt; a method of obtaining a carbonate ester by reacting phosgene with an alcohol; after adding carbon disulfide to the alcohol; Examples include a method of obtaining xanthate by reacting alkyl iodide; a method of obtaining amine oxide by reacting tertiary amine with hydrogen peroxide or carboxylic acid; a method of obtaining selenoxide by reacting orthoselenocyanonitrobenzene with alcohol.

-Polymers (II) to (III) and Polymer (I)-
The main chain of the polymers (I) to (III) (the polymer having a partial structure represented by the general formulas (I) to (III)) is not particularly limited and may be arbitrarily selected depending on the purpose. A suitable polymer can be selected, but a rigid aromatic polymer is preferred. The said polymer may be used individually by 1 type, and may use 2 or more types together.
Examples of the aromatic polymer include polyaniline, polypyrrole, polyacetylene, poly (phenylacetylene), polydiacetylene, polyphenylene (para, meta, ortho), polynaphthalene, polyanthracene, polypyrene, polyazulene, polythiophene, polyselenophene, poly Examples include isothianaphthene, polyphenylene sulfide, polyphenylene oxide, and polyphenylene vinylene. These may be homopolymers or copolymers.

When at least one of the partial structure represented by the general formula (II) and the partial structure represented by the general formula (III) has a polyphenylene structure as a main chain, examples of the partial structure include the following: Examples include the structure. In the following structure, one of X and Y represents a hydrogen atom, and the other represents the above-mentioned leaving substituent.

More specifically, examples of the partial structure represented by the general formula (II) and the partial structure represented by the general formula (III) include the following structures.

As described above, by applying external energy, the exemplary compounds (1) to (11) are converted into the following structures, which are specific examples of the partial structure represented by the general formula (I).
An organic layer containing the polymer (I) in a desired form can be obtained by applying the polymer (II) and polymer (III) before conversion, forming and processing, and applying external energy.

[Synthesis Example of Polymer (II) and Polymer (III)]
Further, specific methods for deriving the synthesis examples of the polymer used in the present invention from the monomers are disclosed, but the synthesis method according to the present invention is not limited to these synthesis examples.

Below, an example of the manufacturing method of polymer (II) and polymer (III) is shown.
Here, Tf represents a trifluoromethylsulfonyl group.

-Monomer production example-
It is possible to produce the [Step 1] azobisisobutyronitrile (AIBN) and N- bromosuccinimide (NBS) compound bromination using brominated or Br ₂ with (1) from the compound (2) .
[Step 2] A general esterification method or etherification method can be used. For example, it can also be formed by using tetramethylammonium hydroxide pentahydrate and R-COOH, or using DBU, base, and R-COOH. can do. It is also easy to form an alkoxy group by using Williamson ether synthesis. Thereby, for example, a compound (3) can be formed as a compound having an acyloxy group used in the present invention.
[Step 3] Compound (5) is obtained by Suzuki coupling of dibromodiiodobenzene (4) and diboron. As the diboron, diboron esters are preferably used. For example, bis (catecholate) diboron, bis (hexylene glycolate) diboron, bis (pinacolato) diboron, bis (neopentyl) diboron and the like are preferably used.
[Step 4] Compound (6) can be produced from Compound (5) by Suzuki coupling reaction with diiodobenzene.
[Step 5] Similarly to step 3, compound (7) can be produced from compound (6).
[Step 6] Compound (8) can be produced by Suzuki coupling reaction of compound (3) having an acyloxy group and diboron (7).
[Step 7] Compound (9) can be produced by a Suzuki coupling reaction of diboron dibromo compound (5) and a biphenylboronic acid compound.
[Step 8] Compound (9) is lithiated by adding organic lithium, for example, n-BuLi, in a dehydrated cryogenic state, and reacted with trimethyltin chloride, whereby trimethyltin body (10) can be obtained.
Thereby, an example of the monomer used by this invention can be manufactured.

-Polymer production example-
-Production Example 1-
The copolymer (8-1) can be synthesized by using the Suzuki coupling reaction of the compound (8) and diboronic acid described above.

-Production Example 2-
By using the Suzuki coupling reaction of the aforementioned compound (8) and diboron, homocoupling can be carried out to obtain the polymer (8-2). The polymer (8-2) can also be obtained by using the Yamamoto reaction using the compound (8).

--- Production Example 3--
A copolymer (8-3) can be obtained by using the Stille coupling reaction of the compound (8) and the compound (10) described above.

Hereinafter, the polymerization method of the polymer will be described in more detail.
Examples of the production method of the polymer (II) and the polymer (III) include methods such as electric field polymerization, oxidative polymerization, and chemical polymerization. However, the chemical polymerization method is preferable in that a polymer soluble in a solvent is easily obtained.

In order to produce the polymer (II) and the polymer (III), a monomer is required, and the monomer can be produced by a general organic synthesis.
In the polymer production method, as the condensation polymerization method, a known condensation reaction can be used depending on the substituent involved in the condensation polymerization. For example, a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Stille coupling reaction, a method of polymerizing by a nickel zero-valent complex (Ni (0) complex), FeCl ₃ or the like Well-known methods such as a method of polymerizing with an oxidizing agent and a method of electrochemically oxidatively polymerizing are exemplified.
Among these, the method of polymerizing by Suzuki coupling reaction, the method of polymerizing by Grignard reaction, the method of polymerizing by Stille coupling reaction, and the method of polymerizing by nickel zero-valent complex are preferable in terms of easy structure control.

The application step is a step of applying a solution.
The solution contains at least a polymer having a partial structure represented by the general formula (II) or a polymer having a partial structure represented by the general formula (III), and further contains other components as necessary. Including.
By the coating process, the organic film can be formed by a wet process.

There is no restriction | limiting in particular as an object which apply | coats the said solution, According to the objective, it can select suitably, For example, organic thin film layers, such as a substrate (support body), a PEDOT / PSS layer, a polymer layer, a metal layer, a metal Examples thereof include an oxide layer. Further, another organic layer may be further laminated on one organic layer (an organic layer containing the polymer (I)).
Examples of the substrate (support) include plastics, metal, silicon wafer, and glass.
As the PEDOT / PSS layer, for example, poly (3,4-ethylenedioxythiophene) (PEDOT) is coated with a conductive polymer aqueous solution doped with polystyrene sulfonic acid (PSS) and heated (for example, at 200 ° C.). 15 minutes).
Examples of the metal forming the metal layer include gold, silver, copper, chromium, platinum, aluminum, nickel, molybdenum, and tungsten.
Examples of the metal oxide that forms the metal oxide layer include silicon oxide, aluminum oxide, iron oxide, ruthenium oxide, zinc oxide, and indium oxide.
The method for applying the solution is not particularly limited and may be appropriately selected depending on the purpose. For example, the spin coating method, the casting method, the dip method, the ink jet method, the doctor blade method, the screen printing method, and the vacuum deposition method. A known film forming method such as sputtering can be used. Thereby, the organic film containing the polymer (II) or the polymer (III) excellent in strength, toughness, durability, etc. without cracks (hereinafter referred to as “precursor-containing film”). Is possible).

-Other ingredients-
Examples of other components included in the solution as needed include organic solvents, organic polymers, inorganic materials, and surfactants.
Examples of the organic solvent include aromatic solvents which may have an alkoxy group or a halogen group such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, anisole, chlorobenzene, dichlorobenzene and chlorotoluene; dichloromethane, dichloroethane, chloroform Halogenated hydrocarbon solvents such as carbon tetrachloride, tetrachloroethane, trichloroethane; ether solvents such as dibutyl ether, tetrahydrofuran, dioxane; methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, cyclohexanol, Linear or branched alcohol solvents such as methyl cellosolve, ethyl cellosolve, ethylene glycol, benzyl alcohol; butylbenzene, cyclohexyl Benzene, tetralin, alkyl-substituted aromatic solvents linear or branched alkyl group of 4 or more carbon atoms which may have a dodecyl benzene.
Examples of the organic polymer include polystyrene, polyethylene, polypropylene, polyester, and polyurethane. Furthermore, organic semiconductor materials such as polythiophene, polyphenylene, polyphenylene vinylene, polycarbazole, polyfluorene, and the like can be given.
As said inorganic material, an inorganic filler etc. are mentioned, for example.

(Laminated electronic devices)
The multilayer electronic device of the present invention is a multilayer electronic device manufactured by the method for manufacturing a multilayer electronic device of the present invention, and includes at least one organic layer (an organic layer containing the polymer (I)). In addition, other layers and other members are included as necessary.
The multilayer electronic device of the present invention includes at least one organic layer including at least one of the polymer (II) and the polymer (III), and further includes other layers and other as required. Includes members.
The laminated electronic device and the organic layer contain at least one of the polymer (II) and the polymer (III), which are polymers before conversion, as impurities. The inclusion of these polymers (II) and polymers (III) is, for example, infrared absorption spectrum, microscopic Raman spectrum, gas chromatography, liquid chromatography, MALDI method (matrix-assisted laser desorption ionization method) Etc. can be analyzed by a mass spectrometry method using the like.
It is preferable that the laminated electronic device is any one of a field effect transistor, electroluminescence, and a thin film solar cell.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.

(Production of organic film)
Exemplified compound 1 represented by the following structural formula (1) (before conversion) was dissolved in toluene to prepare an ink containing 1% by mass of exemplified compound 1 (before conversion). Next, the ink was spin-coated on quartz glass at a rotation speed of 1,000 rpm to produce a thin film containing Exemplary Compound 1 (before conversion). The obtained thin film was baked for 30 minutes on a hot plate (surface temperature 250 ° C.) in a glove box (MBRAUN, Ar atmosphere) (hereinafter referred to as “GB”), and cooled to room temperature. An organic film containing Exemplified Compound 1 (after conversion) represented by Structural Formula (1 ′) was obtained.

The obtained organic film was peeled off and attached to a plate for MALDI-TOFMS, and MALDI-TOFMS measurement of Example Compound 1 (after conversion) was performed. The results are shown in FIG.
The MALDI-TOFMS measurement was performed using a MALDI-TOFMS apparatus (manufactured by Bruker, AUTOFLEX) without adding a matrix.
Further, TG-DTA (simultaneous measurement of differential heat and thermogravimetry) and DSC (thermal analysis) were measured using about 5 mg of the powder of Exemplified Compound 1 (before conversion). The results are shown in FIG. In FIG. 2, the horizontal axis indicates the temperature, and the vertical axis indicates the weight reduction rate and the amount of heat, respectively.
The TG-DTA (simultaneous differential heat / thermogravimetric measurement) and DSC (thermal analysis) measurements were made using a TG-DTA apparatus (TG / DTA7200) and DSC apparatus (X-DSC7000) manufactured by Seiko Instruments Inc. I went.
From these results, it was confirmed that the target exemplified compound 1 (after conversion) was obtained.

Example 1
<Production of electroluminescence element>
Conductive polymer aqueous solution (PEDOT / PSS) (manufactured by HC Stark Co., Ltd.) in which poly (3,4-ethylenedioxythiophene) (PEDOT) is doped with polystyrene sulfonic acid (PSS) on an ITO substrate Apply at 000 rpm for 30 seconds. B. Heated at 200 ° C. for 15 minutes. Subsequently, a tetrahydrofuran (THF) solution containing 5% by mass of Exemplified Compound 1 (before conversion) was spin-coated thereon at a rotational speed of 1,000 rpm for 30 seconds. Then G. B. The organic layer containing Example Compound 1 (after conversion) was obtained by heating at 280 ° C. for 30 minutes in an argon atmosphere. Furthermore, the electroluminescent element (electrode) of Example 1 was formed by apply | coating nanometal Ag (made by Harima Kasei Co., Ltd.) as a cathode at 1,000 rpm, and heating at 150 degreeC.
When the obtained electroluminescence device was irradiated with excitation light of 365 nm, blue-green light emission was observed.

(Example 2)
<Fabrication of field effect transistor>
A UVO ₃ treated Si (n-doped, oxide film, HMDS treated, 10 mm * 10 mm) substrate was prepared, and a vacuum evaporation apparatus (manufactured by Seinan Industry Co., Ltd., back pressure 5) was used as a source electrode and a drain electrode. Au was vacuum-deposited at 5 × 10 ⁻⁴ Pa) (5 Å / s). At that time, the channel length of the vacuum deposition apparatus was 2,000 μm and the channel width was 100 μm. A THF solution containing 5% by mass of Exemplified Compound 1 (before conversion) was spin-coated at a rotational speed of 1,000 rpm for 30 seconds. B. The organic layer (semiconductor active layer) containing exemplary compound 1 (after conversion) was formed by heating at 280 ° C. for 30 minutes in an argon atmosphere. On top of that, a 7% by mass solution of thermally crosslinkable polyimide (CT4112, manufactured by Kyocera Chemical Co., Ltd.) was applied as an insulating film at 1,000 rpm, 1 hour at 80 ° C., 1 hour at 120 ° C., and 1 hour at 200 ° C. Heated.

  Thereafter, nanometal Ag (manufactured by Harima Chemical Co., Ltd.) was applied as a gate electrode at 1,000 rpm, and heated at 150 ° C. to form a gate electrode. Thereby, the field effect transistor device of Example 2 was obtained.

As a result of measuring the transfer characteristics of the obtained field effect transistor device using semiconductor parameters (B1500A, manufactured by Agilent Technologies, Inc.), when the SD voltage was measured from 40V to -40V with a gate voltage of -40V. The mobility was μ = 5 × 10 ⁻³ cm ⁻¹ / Vs, and the Vth = −21 V On / Off ratio was 10 ⁵ . From this result, it became clear that semiconductor characteristics were obtained with the coated laminated device.

(Example 3)
<Production of thin film solar cell>
On the ITO substrate, PEDOT / PSS (manufactured by HC Stark) was applied at 2,000 rpm for 30 seconds. B. Heated at 200 ° C. for 15 minutes. Next, a THF solution containing 5% by mass of Exemplified Compound 1 (before conversion) is spin-coated at a rotation speed of 1,000 rpm for 30 seconds. B. The organic layer (intermediate layer) containing the exemplary compound 1 (after conversion) was obtained by heating at 280 ° C. for 30 minutes in an argon atmosphere. Then, a dichlorobenzene solution containing 1% by mass of poly-3-hexylthiophene (P3HT) (manufactured by Merck) and 0.3% by mass of phenyl C61 butyric acid methyl ester (PCBM) (manufactured by Frontier Carbon Corporation) at 1,000 rpm. A film was formed by spin coating for 30 seconds. Then, it heated at 150 degreeC for 10 minute (s). Furthermore, aluminum was vacuum-deposited as a cathode with a vacuum deposition apparatus (manufactured by Seinan Industry Co., Ltd., back pressure 5 × 10 ⁻⁴ Pa) (5 Å / s). Thereby, the thin film solar cell of Example 3 was obtained.

(Comparative Example 1)
In Example 3, a thin film solar cell of Comparative Example 1 was produced in the same manner except that Exemplified Compound 1 (before conversion) was not applied.

As evaluation of the obtained thin film solar cell of Example 3 and Comparative Example 1, IV measurement was performed using a simulated sunlight irradiation device while irradiating simulated sunlight with a sunlight standard spectrum AM1.5.
The photoelectric conversion efficiency of the thin-film solar battery of Comparative Example 1 was 2.8% (FF0.51). On the other hand, in the thin film solar cell of Example 3 (when Example Compound 1 was used as the intermediate layer), the photoelectric conversion efficiency was 3.2% (FF 0.55).

As an aspect of this invention, it is as follows, for example.
<1> A method for producing a laminated electronic device including at least one organic layer,
A coating step of coating a solution containing at least one of a polymer having a partial structure represented by the following general formula (II) and a polymer having a partial structure represented by the following general formula (III);
A moiety represented by the following general formula (I) is at least one of a polymer having a partial structure represented by the general formula (II) and a polymer having a partial structure represented by the general formula (III). An organic layer forming step of forming the organic layer containing a polymer having a partial structure represented by the general formula (I) by converting into a polymer having a structure;
It is a manufacturing method of the multilayer electronic device characterized by including.
[In General Formula (I), Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring. It may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or An aryl group, m represents the number of modifications to the benzene ring forming the main chain, is an integer of 1 to 4, and when n ≧ 2, R _{1 to} R ₄ may be the same as each other If m ≧ 2, R _{1 to} R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]
[In general formulas (II) and (III), _one of X ₁ and Y ₁ is a hydrogen atom, the other is a leaving substituent, one of X ₂ and Y ₂ is a hydrogen atom, and the other is a leaving atom. One of X ₃ and Y ₃ is a hydrogen atom, and the other is a leaving substituent, and each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted group. A substituted acyloxy group, Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring; , Which may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl M is the benzene ring that forms the main chain Indicates the number of modifications, an integer from 1 to 4, provided that when n ≧ _2, or different to R 1 to R ₄ may each be identical to each other, the case of m ≧ _2, R 1 ~R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]
<2> The method for producing a laminated electronic device according to <1>, wherein the organic layer forming step is performed at 25 ° C. to 500 ° C.
<3> A multilayer electronic device manufactured by the method for manufacturing a multilayer electronic device according to any one of <1> to <2>.
<4> A laminated electronic device comprising at least one of a polymer having a partial structure represented by the following general formula (II) and a polymer having a partial structure represented by the following general formula (III): It is.
[In general formulas (II) and (III), _one of X ₁ and Y ₁ is a hydrogen atom, the other is a leaving substituent, one of X ₂ and Y ₂ is a hydrogen atom, and the other is a leaving atom. One of X ₃ and Y ₃ is a hydrogen atom, and the other is a leaving substituent, and each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted group. A substituted acyloxy group, Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring; , Which may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl M is the benzene ring that forms the main chain Indicates the number of modifications, an integer from 1 to 4, provided that when n ≧ _2, or different to R 1 to R ₄ may each be identical to each other, the case of m ≧ _2, R 1 ~R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]
<5> The multilayer electronic device according to any one of <3> to <4>, which is any one of a field effect transistor, electroluminescence, and a thin film solar cell.

Japanese Patent No. 3733527 JP2012-041327A JP 2012-216669 A

Journal of the American Chemical Society. 2008, 130, 4216-17. Nature Vol 466, 470-473. Macromolecules 2000, 33, 5634. Journal of the American Chemical Society. 2004, 126, 9487. Macromolecules, 1993, 26, 2607. Journal of the American Chemical Society. 1992, 114, 3169.

Claims (4)

A method for producing a laminated electronic device comprising at least one organic layer,
A coating step of coating a solution containing at least one of a polymer having a partial structure represented by the following general formula (II) and a polymer having a partial structure represented by the following general formula (III);
A moiety represented by the following general formula (I) is at least one of a polymer having a partial structure represented by the general formula (II) and a polymer having a partial structure represented by the general formula (III). An organic layer forming step of forming the organic layer containing a polymer having a partial structure represented by the general formula (I) by converting into a polymer having a structure;
A method for manufacturing a laminated electronic device, comprising:
[In General Formula (I), Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring. It may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or An aryl group, m represents the number of modifications to the benzene ring forming the main chain, is an integer of 1 to 4, and when n ≧ 2, R _{1 to} R ₄ may be the same as each other If m ≧ 2, R _{1 to} R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]
[In general formulas (II) and (III), _one of X ₁ and Y ₁ is a hydrogen atom, the other is a leaving substituent, one of X ₂ and Y ₂ is a hydrogen atom, and the other is a leaving atom. One of X ₃ and Y ₃ is a hydrogen atom, and the other is a leaving substituent, and each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted group. A substituted acyloxy group, Q _{1 to} Q ₆ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and adjacent groups may be bonded to each other to form a ring; , Which may be condensed with an adjacent benzene ring, n represents a repetition and is an integer of 0 to 5, and R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, or an aryl M is the benzene ring that forms the main chain Indicates the number of modifications, an integer from 1 to 4, provided that when n ≧ _2, or different to R 1 to R ₄ may each be identical to each other, the case of m ≧ _2, R 1 ~R ₄ , n, and Q _{1 to} Q ₆ may be the same as or different from each other. ]   The method for producing a laminated electronic device according to claim 1, wherein the organic layer forming step is performed at 25 ° C. to 500 ° C. A laminated electronic device comprising at least one of a polymer having a partial structure represented by the following general formula (II) and a polymer having a partial structure represented by the following general formula (III).
[In the general formulas (II) and (III), X ₁ And Y ₁ One of which is a hydrogen atom, the other is a leaving substituent, and X ₂ And Y ₂ One of which is a hydrogen atom, the other is a leaving substituent, and X ₃ And Y ₃ One of which is a hydrogen atom and the other is a leaving substituent, and each of the leaving substituents is independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted acyloxy group, and Q ₁ ~ Q ₆ Are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and may be bonded to each other to form a ring, or condensed with an adjacent benzene ring. N is an integer from 0 to 5, ₁ ~ R ₄ Each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, m represents the number of modifications to the benzene ring forming the main chain, is an integer of 1 to 4, and when n ≧ 2 , R ₁ ~ R ₄ May be the same as or different from each other, and when m ≧ 2, R ₁ ~ R ₄ , N, and Q ₁ ~ Q ₆ May be the same as or different from each other. ] The multilayer electronic device according to claim 3, which is any one of a field effect transistor, electroluminescence, and a thin film solar cell.