TW201231491A - Compound and film containing the same - Google Patents

Abstract

This invention provides a compound having &pgr; conjugated structure, useful for an organic semiconductor layer of an organic transistor, and a film using this compound, as well as a precursor compound used for obtaining the compound having &pgr; conjugated structure. The said compound has a structure unit represented by formula (1) and a structure unit having &pgr; conjugated structure. [wherein, R1 and R2 respectively individually represents a substitute, R3 and R4 respectively individually represents hydrogen atom or a substitute, m and n respectively individually represents an integer of 0 to 3, Y represents a-divalent group. When R1 is plural, the plurality of R1 may be the same or different. When R2 is plural, the plurality of R2 may be the same or different.]

Description

201231491 6. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a compound and a film containing the same. [Prior Art] In the manufacturing process of an organic semiconductor element such as an organic transistor, a high-temperature step and a vacuum step necessary for the manufacture of an inorganic semiconductor element such as a lanthanide transistor can be omitted, and the manufacturing requirement can be reduced. energy. Further, the organic semiconductor element may become a flexible film-like element, and is attracting attention as a next-generation element. A compound having a 7 Å co-consumption structure exhibits conductivity and semiconductivity, and has been attracting attention as an organic semiconductor compound used in an organic semiconductor element. A compound having a structure of 7 Å is specifically known as a poly 3-hexyl group. Poly 3 - hexylthiophene (P3HT) and the like. Non-Patent Document 1 discloses an organic transistor in which a gas-like solution of poly-3-hexylthiophene is spin-coated on a Si 1 icon wafer to form an organic semiconductor layer. However, the above-described organic transistor has insufficient crystal characteristics, and a useful new specification organic semiconductor compound has been sought for the organic semiconductor layer of the organic transistor. In Non-Patent Document 2, a compound having a 7-inch conjugated structure is described as a copolymer of polyanthracene, hydrazine, and benzene. The ruthenium portion is mostly luminescent, and has a part of a 7-inch conjugated structure of a ruthenium partial polymer, which is a material exhibiting high possibility of electroluminescence.

323797 S 201231491 Compounds with a 7-inch conjugated structure are mostly insoluble, and the synthesis method is easily complicated. Therefore, in Non-Patent Document 2, it is proposed to change the copolymer of polyfluorene, hydrazine, and benzene by heating to exhibit a solubility in a solvent. The above precursor, for the polyfluorene, or the copolymer of hydrazine and benzene [previously anhydrous rhododendron is a structure added by Diels-Alder. [Non-Patent Document] Non-Patent Document 1: Lett.) ’ Volume 53,

Commun.) Section [Summary of the Invention]

Applied Physics Letters (Appl. Phys. No. 18, pp. 195-197 (1988) 2 : Chemical Communication (Chem. 74 (1997) (The textbook to be solved by the invention is issued in September; g organic crystal The object of the above-mentioned problems is to provide a film containing a compound and a compounded conjugated structure having a π-conjugated structure, which is contained in a semiconductor semiconductor layer, and a method for obtaining the same. (Precursor compound for solving the problem of the subject matter), h is provided for the structural unit represented by the formula (1)

323797 5 201231491 [In the formula, Ri and R2 are each independently and independently represent a hydrogen atom or a substituent. Daiji. R and R4, each to an integer of 3. γ represents the divalent group. : From independence, 〇 can also be different. When R2 is plural, these can be the same or different. ], a structural unit represented by the formula (2), (3), or (4)

The formula (1) to (4) towel 'R5 represents a substituent. s represents the integer from i to 4 - p t: an integer from 0 to 4. q represents an integer from 〇 to 4. When R5 is plural, the 4s may be the same or different. 〕,

The structural unit represented by the formula (5) —^—Ar1 (5)

[wherein Ar represents -CsC-, -C (RA) =C (RA) -, -N -N-, a C (RB) =N-, and may have a substituent with a ring number of 8 or more a aryl group or a heteroaryl group which may have a substituent. However, Arl is not a base of the above formula (1). Two RAs, each independently, represent a hydrogen atom or a substituent. RB represents a hydrogen atom or a substituent. ], and the structural unit represented by the following formula (6) 6 323797 201231491 Αγ2-Ν Bu 3——士 Ar4_

Ar5 Ar6

Ar 7 hopper (6) [wherein, r and rr each represent the number of structural units (_Ar3 - NAr6_) and the number of structural units it ( - Ar -NAr7 -), which are independent, respectively, or are Ar2, Ar3, Ar4 And Ar5, each independently, represents an extended aryl group which may have a substituent or a heteroaryl group which may have a substituent.

Ar, Ar and Ar8, each independently, represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. ] = a compound of at least one structural unit selected in groups. In the above formula (1), the benzene ring on the left side is different from the two carbon atoms on the right side (one of these is bonded to R3, and the other is bonded to r4). Any one of the benzene ring carbon atoms may be substituted with the (10) R1 group ' of the nitrogen atom and one adjacent structural unit (not shown) 2 . Similarly, in the above formula (1), s R5 groups are substituted for each chlorine ', respectively, except for two ring carbon atoms to which a neighboring structural unit (not shown) is bonded, or two of the other ring carbon atoms, that is, S ring two sons, .,. :: Other formulas of the similar formula (1) and formula (1) are also explained in the same manner. Indicates that 24Mi _ has 2 (four) above equations (1) and W 70. At this time, the structural units represented by the formula (1) are identical to each other or may be different. It is said that it is possible to be between each other. 323797 7 201231491 _In a certain form, the above compound has more than one structural unit represented by the above formula (?)

In a certain form, Y represents a divalent group selected from at least one group of groups represented by the formula (γ-D to (Y-8).

[In the formula (Y-1) to (γ-8), R1. To the reference: f

: indicates a chlorine atom or a substituent. I means that the gas atom or the prime element = two = the same can also be different. In other words, when the front axis has one structural unit represented by the formula (1), the above formula (Υ-υ to (γ - 8) is used for any one of the formulas:" has two or more formulas (1). Structure, : : The Υ of the order may be the same or different from each other. When the 冓 is in a certain form, the compound is a polymer compound having a weight of more than 3,000. When the amount is 3000, in a certain form, The aforementioned compound, and has the formula (1)

323797 S 201231491

Wherein n, m, R1, R2, R3 and R4 have the same meanings as in the formula (1). 〕 indicates the structural unit. Furthermore, the present invention provides a solution containing any of the foregoing compounds and a solvent. Further, the present invention provides a film containing any of the foregoing compounds. Furthermore, the present invention provides a laminate having a substrate and a film, wherein the film is coated on the substrate to form a coating film containing a compound containing the structural unit represented by the formula (1), and secondly, the coating film is added. And at least a part of the whole of the compound containing the structural unit represented by the formula (1) contained in the coating film, and the structural unit represented by the formula (1) is converted into the structural unit represented by the formula (8) And the film obtained. Furthermore, the present invention provides a method for producing a laminate having a film and a substrate, comprising the steps of: applying the solution to a substrate to form a coating film containing a compound containing the structural unit represented by the formula (1), The coating film is added with energy so that at least a part of the entire compound containing the structural unit represented by the formula (1) contained in the coating film is converted into a structural unit represented by the formula 9 323797 201231491 (1). The step of forming a film by the structural unit represented by the formula (8). (Effect of the Invention) A compound having a 7-inch conjugated structure and a film containing the compound, and a precursor compound for obtaining a compound having the 7-inch structure can be provided, which are useful in an organic semiconductor layer of an organic transistor. [Embodiment] Hereinafter, the present invention will be described in detail. The compound of the present invention contains a structural unit represented by the formula (1).

In the formula (1), R1 and R2 each independently represent a substituent. Among the substituents, a halogen atom and a carbon number of 1 to 30 are preferred. For halogen atoms, examples include a deficient atom, a chlorine atom, a desert atom, and a moth atom. Among them, a fluorine atom or a chlorine atom is preferred. The base of carbon number 1 to 30, such as ethyl, butyl, hexyl, octyl, decyl, etc. alkyl, decyloxy, ethoxy, butoxy, hexyloxy, octyloxy, twelve An alkoxy group such as a oxy group, a heteroaryl group such as a thienyl group, an aryl group such as a phenyl group or a naphthyl group, or a cyano group. The hydrogen in the group having 1 to 30 carbon atoms may be substituted by a halogen atom. When a hydrogen atom in a group having 1 to 30 carbon atoms is substituted with a halogen atom, the halogen

10 323797 S 201231491 It is preferred to replace the fluorine atom with a fluorine atom. η and m, each independently, represent an integer from 0 to 3. η and m are preferably 0. When R1 is plural, the same may be the same or different. When R2 is plural, the same may be the same or different. In the formula (1), R3 and R4 represent a hydrogen atom or a substituent. Examples of the substituent represented by R3 or R4 include the same substituents as those represented by R1. From the viewpoint of easiness of compound synthesis, R3 and R4 are preferably a hydrogen atom. In the formula (1), Y represents a divalent group. Among the two valence groups, it is preferable to add energy such as heat and light to be separated. The two-valent group represented by Y is exemplified as the following.

In the formula (Y-1) to the formula (Y-8), R1() to R2° are the same or different and each represents a hydrogen atom or a substituent. Among them, a hydrogen atom or a group having 1 to 30 carbon atoms is preferred. When R1() to R19 are a substituent, examples of the substituent include a group such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a decyloxy group, an ethoxy group, and a butoxy group. An alkoxy group such as a hexyloxy group, an octyloxy group or a dodecyloxy group; an aryl group such as a phenyl group or a naphthyl group; The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Preferably, when R2 is a substituent, examples of the substituent include, for example, anthracenyl group, ethyl group, 11 323797 201231491 butyl group, hexyl group, octyl group, dodecyl group, etc., f-oxyethoxy group, butyl group An alkoxy group such as an oxy group, a hexyloxy group, an octyloxy group or a dodecyloxy group; an aryl group such as a phenyl group or a naphthyl group; and a vinyl group having an ester structure; Those who are atomic, such as fluorine shoulders, chlorine atoms, desert atoms, iodine atoms. Among the dentate atoms, a chlorine atom or a desert atom is preferred, and a gas atom is preferred. Among the groups represented by the formula (Y 1) to the formula (Y-8), the group represented by the formula (γ-3) to the formula (Y-7) is preferred, and the formula (γ-3) to the formula (γ-5) The basis of the table is preferred. For example, preferred lanthanum is in the formula (Υ-3) or the formula (γ-4), ΙΤ, γ, "and Rl9, which are alkoxy groups having a carbon number of 1 to 1 Å, in particular, a carbon number 丨The compound of the present invention has a structural unit represented by the formula (1), 2 and a structural unit having a π-co-subtraction structure. Specific examples of structures having a π(tetra) structure include At least one structural unit of the group represented by the following structural formula (1), the structural unit represented by the formula (3), the structural unit represented by the formula (4), the structural unit represented by the formula (5), and the structural unit represented by the formula (4) ^ #

201231491

In the formulae (2) to (4), R5 represents a substituent. Examples of the substituent represented by R5 include the same substituents as those of the substituent represented by R1. In the formula (2), s represents an integer of 1 to 4. Wherein p represents an integer from 0 to 4. p is better. In the formula (4), q represents an integer from 〇 to 4. q is better. In the formulae (2) to (4), when R5 is plural, the same may be the same or different. In the formula (5), Ar 丨 represents a CsC—, a C(RA)=:C(RA)—, N—N—, a c (rb), a ring having a ring number of 8 or more. a base or a heteroaryl group which may have a substituent. However, Arl is not represented by the above formula (\). Two RAs each independently represent a hydrogen atom or a substituent. RB represents a hydrogen atom or a substituent. The example in which the substituent is represented by ^ or RB is the same as the substituent of the substituent represented by R1. Examples of the aryl group include a group in which two hydrogen atoms are removed from a single-ring aromatic hydrocarbon, two hydrogen atoms are removed from a polycyclic aromatic hydrocarbon, and two or more aromatic hydrocarbons are directly bonded or intercalated. The vinyl group (the compound of v removes 2 money base. When the exudation group is a group in which two hydrogen atoms are removed from a single-ring aromatic hydrocarbon, 323797 13 201231491 = the carbon number of the extended aryl group is preferably 8 to 6G. 8 to 48 is preferred, and 8 to 3 〇'., and more preferably '8 i 14 is particularly preferred. The carbon number does not contain the carbon number of the substituent. When the polycyclic aromatic hydrocarbon removes two hydrogen atoms , =:: 1〇至6〇 is better, 1〇至48 is ου冯更佳, 1〇至14 王伸芳A is the carbon number of the guest without the substituent. It can be taken; : For the case of two nitrogen atoms, RR], the following groups are listed.

' R, R R R

R 5

R R R 6

R R R R

R R R

323797 s 14 10 9 201231491

15 323797 201231491

In the above formula, R each independently represents a hydrogen atom or a substituent. When R is a substituent, an alkyl group such as a methyl group, an ethyl group, a butyl group, a 2-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group or a hexadecanyl group is exemplified, and an oxime group or an ethyl group is exemplified. An alkoxy group such as a butyl group, a butoxy group, a hexyloxy group, an octyloxy group or a decyloxy group; a phenyl group; an aryl group such as a naphthyl group; a heteroaryl group such as a thienyl group; a halogen atom; and a cyano group. When R is an alkyl group, it is preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having a carbon number of 12 to 12: preferably, an alkyl group having 1 to 8 carbon atoms is more preferably when R is an alkoxy group. The alkoxy group having 1 to 20 carbon atoms is preferred, the alkoxy group having a carbon number of 12 to 12 is preferred, and the alkoxy group having 1 to 8 carbon atoms is more preferred. When the aryl group is a group in which two hydrogen atoms are directly bonded or a compound in which an ethylene group is bonded by a vinyl group, the aromatic hydrocarbon is preferably benzene. The aryl group is an example in which two or more benzene groups are directly bonded or a group in which two hydrogen atoms are removed by a vinyl-bonding compound, and examples of the exoaryl group having a substituent may be mentioned, and the following groups are listed.

323797 17 201231491 R R R b〇 ^

R R R R

R R

In the above formula, 'R means the same meaning as described above. Examples of the heteroaryl group include a group in which two hydrogen atoms are removed from a monocyclic aromatic heterocyclic compound, and two chlorine-containing shoulder groups are removed from a polycyclic aromatic heterocyclic compound, and two or more Aromatic heterocyclic compounds 323797

S 18 201231491 The scented compound is directly bonded or removed by a vinyl-bonded compound to remove two nitrogen atom groups. ' The carbon number of the heteroaryl group when the base of two hydrogen atoms is removed by a monocyclic aromatic heterocyclic compound or the base of two hydrogen atoms is removed by a polycyclic aromatic heterocyclic compound. It is preferably from 3 to 60, and preferably from 3 to 2 is preferred. This carbon number does not contain the carbon number of the substituent. When the heteroaryl group is a group in which two nitrogen atoms are removed from a monocyclic aromatic heterocyclic compound or two hydrogen atoms are removed from a polycyclic aromatic heterocyclic compound, a heteroaryl group which may have a substituent is exemplified. , listed as the following two

323797 19 201231491

20 323797 s 201231491

21 323797 201231491

22 323797 s 201231491

23 323797 201231491 R R R r

D R R R R

129 In the above formula, R represents the same meaning as described above. =heteroaryl group may have a substituent when the two or more hydrogen atoms are bonded directly or in combination with a compound of at least one aromatic heterocyclic compound. Examples of heteroaryl groups include the following groups.

R R R R

R

323797 24 201231491

148 149

R R

R R

151 25 323797 201231491

R

The clothes are not prosperous, and the black nitrogen atoms are formed. When L is plural, it may be represented by ==, or "extended heteroaryl group which may have a substituted ring carbon number of 8 and a shirt substituent. "The group may have the formula (6), Ar2, Ar3 And Ar4 and red 5 each independently represent an extended aryl group which may have a substituent or a heteroaryl group which may have a substituent. Examples of the aryl group and the heteroaryl group are as shown in the example of a phenyl group, which is the same as the one represented by Ari, which is represented by the extension of 26 323797 % 201231491.

Ar2, Ar3, Ar4 and Ar5 are preferably a phenyl group which may have a substituent. In the formula (6), Ar6, Ar7 and Ar8 each independently represent an aryl group which may have a substituent or a heteroaryl group which may have a substituent. Examples of the aryl group include, for example, a strepyl group, a naphthyl group, and an anthracenyl group. Examples of heteroaryl groups are exemplified by porphinyl groups.

Ar6, Ar7 and Ar8' are each independently, and a phenyl group which may have a substituent is preferred, and a phenyl group which may have an alkyl group is preferred. Equation (6), r and rr, respectively, indicate the number of structural units (_red-) and the number of structural units (-Ar5-MAr*7, A, dry u, Ar Mr-1), each independently, being 0 or 1. a carbon atom in the group represented by r, Ar, Ar or Ar8, a red atom bonded to a nitrogen atom bonded to a group represented by Ar5, Ar6, Ar7 or Ar«, and a red, 2, 5, 5 or 7 Indicates that the carbon atoms in the group are directly bonded, or may also be referred to by a 〇-, -s-, -~~ ^ \ ~ \)) -, a c (, -〇_, -N(RC)-, - c(, -N(8)- or -:(8)2: combines to form a 5- to 7-membered ring, which represents an alkyl group, an aryl group, a heteroaryl group or a aryl group.

R R

Examples of the structural unit represented by the formula (6) are as follows. R R R R R

323797 158 27 201231491 In the above formula, R represents the same meaning as described above. The compound of the present invention may contain only the structural unit represented by the formula (2) to the formula (6), or may contain two or more kinds. Further, the compound of the present invention may contain more than j structural units represented by the formula (7). (7) The compound of the present invention may further contain one or more structural units represented by the formula (8).

1^, 1^3, and 1^4, which have the same meaning as those in the formula (1). c The compound of the present invention is preferably one containing two or more of the junction loss expressed by the formula (1). The structural units represented by the formula (1) contained may be the same or may be different. The molecular weight of the compound of the present invention is not particularly limited, and it is preferred that the molecular weight is good, but a polymer compound is preferred. The polymer compound in the present invention indicates a weight of 3 x 10 or more in terms of polystyrene (po 1 ystyrene ). - Knife is 1 323797 28 201231491 Among the compounds of the present month, it is preferred to use a molecular compound having a weight average molecular weight of 3χ1〇3 to 1x10. When the weight average molecular weight is more than the above, the film formation in the production of the member (deiee) can suppress the solubility of the solvent at 1x10 or less and the coating property at the time of forming the device. The 4-weight 1 average molecular weight is better, $8><1〇3 to 5χ1〇6', and particularly preferably 1x10 to lxl〇6. In terms of film formation in the production of the member, it is preferably 10,000 or more from the viewpoint of suppressing the occurrence of defects. <The number of styrene conjugates is preferably ΐχ1〇3 to 1χ1〇8, preferably 2χ1()3 to 1χ1 (the average molecular weight of Γ° polystyrene is 1 〇=上上' It is easy to obtain a well-known film. On the other hand, when it is 1 〇8 or less, the solubility of the molecular compound is high, and it is easy to produce a film. The weight average molecular weight in the present invention means the use of gel permeation chromatography (GPC gel permeation). Chr〇mat〇graphy), the weight average molecular weight calculated from the limene standard. A. When the compound of the present invention is a southern molecular compound, from the viewpoint of solubility, the total repeating unit of the polymer compound has eight, 100 In the case of the structure represented by the formula (1) contained in the repeating unit: the amount in the range is preferably from 20 to 99, and preferably from 30 to 60. Early, 4, the same knife, 1匕5, 隹/knife in the chain When the terminal is involved in the polymerization, the polymer compound obtained is used for the organic element because the bucket has a lower b-type, and the terminal is preferably a base which is not related to the polymerization. The stable base molecular chain is stable. The total attenuation of the line has a continuous technique, and the basis of 'σ & Specifically, it is exemplified in Japanese Patent Laid-Open No. 9-454, No. 8, No. 323797 29 201231491, and the substituents described therein are taken as an example. The easiness, when the I-knife is used for the element, the manufacturing element can be made 0. The solubility of the solvent in the street is high. Specifically, it is preferable to have a solubility of 0.1% by weight or more by weight of the solution, and it is preferable to have a solubility of a weight-producing solution. ^The solubility of Ling night is better. Method 7 == 曰 is a polymer compound, the manufacture of the compound. Tanning, but enumerated, such as using a reducing couple using a Ni catalyst =: method, using stiUe coupling The method of the reaction, the method of using Suzuki to synthesize the compound, and the Suzuki coupling reaction method. The conjugate coupling reaction method is preferably a method using a Suzuki coupling reaction, and for example, a compound having one or more compounds represented by the following formula

Qi-E 丨-Q2 (1〇〇) [wherein El represents a structural unit represented by the formula (1). (^ and q2, which are the same or different 'is a butterfly acid residue or a boronic acid ester residue.) and one or more compounds m2-i2 (200) represented by the following formula: wherein E2 represents a formula (2) ) to the structural unit represented by the formula (8). L and T2 are the same or different, and represent a halogen atom, a sulphuric acid S (a 1 ky 1 sulf〇nate) group, an aryl sulfonate (aryl). a sulfonate or a arylalkyl sulfonate group. A method for producing a reaction in the presence of a catalyst and a test. The compound of the formula (200) is used in the reaction of the compound 30 323797 201231491 In total, the total number of moles of one or more compounds represented by the formula (100) is preferably as a surplus, and the total number of moles of one or more compounds represented by the reaction formula is regarded as In the case of 1 mol, the total number of moles of the compound represented by the formula (100) is preferably from 〇6 to 0.99 mol, more preferably from 0.7 to 0.95 mol. In the formula (200), 1 and The halogen atom represented by L is exemplified by a gas atom, a chlorine atom, a bromine atom, and an iodine atom. The bromine atom and the iodine atom are preferred, and the bromine atom is more preferred. In the formula (200), the oxime and the T2 are represented by a non-alkyl group, and the methane sulfonate group and the ethane sulfonic acid are used. The ester group and the trifluorosulfonate group are exemplified. The aryl sulfonate group is exemplified by a benzenesulfonate group and a p-toluenesulfonic acid group. The arylalkyl sulfonate group is used. The benzyl sulfonate group is exemplified. For the catalyst used in the Suzuki coupling reaction, for example, pd ( 〇 > catalyst, Pd (II) catalyst, etc., specific examples of the catalyst are listed. ([Triphenylphosphine)], palladium acetate, dichlorobis(triphenylphosphine), (for the ease of reaction (polymerization) operation, the reaction (polymerization) speed of the dichlorobis (three) Phenylphosphine) palladium (II) or palladium acetate is preferred. The amount of the palladium catalyst to be added is not particularly limited, as long as it is a catalyst, and the compound represented by the formula (10〇) is 1 molar. , usually, 蕙〇. 〇〇〇1 molar to 0. 5 moles, preferably 〇. 0003 Moer to 〇. 丨 Moer is used in the Suzuki coupling reaction, for inorganic testing, Inorganic salts, etc. Inorganic testers, such as barium carbonate, sodium carbonate, gas oxygen, etc. Organic bases, such as triethylamine, tributylamine, etc., such as fluorinated planers, etc. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 It is 1 mol to 10 mol. When the palladium catalyst is a palladium acetate, a phosphorus compound may be added as a ligand (1 i gand ). As examples of the phosphorus compound, there are exemplified by triphenylphosphine-(o-nonylphenyl)phosphine and tris(o-o-oxyphenyl)phosphine. When adding the lining: the amount of the addition, relative to the palladium catalyst 1 mole, usually 0 5 moles to 100 moles, preferably 0. 9 moles to 20 moles, more preferably 丨莫耳To 10 moles.

In the case of the Suzuki coupling reaction, the reaction is usually carried out in a solvent. Examples of the solvent include, for example, N,N-dimethylformamide, toluene, dimethoxyethyl bromide, and tetrahydrofuran. From the viewpoint of solubility of the polymer compound, toluene or tetrakisole is preferred. Further, in the reaction system of the aqueous solution, the monomer can be reacted in a two-phase solvent of the aqueous phase and the organic phase. When a base is used as the inorganic salt, the monomer is usually ruthenium in a 2-phase solvent in a reaction system in which an aqueous solution is added. Further, in the reaction system of the aqueous solution, when the monomer is reacted in the solvent of the two phases, a phase shifting catalyst such as a fourth-order ammonium salt or the like may be added to the reaction system as necessary.

The temperature of the Suzuki coupling reaction depends on the above solvent, but usually it is about 50 ° C to 160 ° C. From the viewpoint of high molecular weight of the polymer compound, it is preferably 6 (TC to 120 t. Further, it is also possible to raise the temperature to the vicinity of the boiling point of the solvent to reflux.

The progress time (reaction time) of the Suzuki coupling reaction can be used as the end point when the degree of polymerization of the target is reached. Usually, it is about 1 hour to 2 hours 323797 32 201231491, preferably about 1 hour to 30 hours.

The Suzuki coupling reaction is carried out in an inert gas atmosphere such as argon or nitrogen, in which the Ib catalyst is not deactivated. For example, argon gas, nitrogen gas or the like is used to carry out sufficient degassing. Specifically, the reaction vessel (reaction system) is sufficiently substituted with nitrogen gas, and after degassing, a compound represented by the formula (100), a compound represented by the formula (200), and dichlorobis(triphenylbenzene) are added to the polymerization vessel. Palladium (II), and the reaction vessel is sufficiently substituted with nitrogen. After degassing, a solvent which is previously ventilated with a gas, degassed, for example, degassed benzene, is added to the solution. The test is carried out by previously bubbling degassing by nitrogen gas, for example, after degassing the aqueous solution of sodium carbonate, heating, raising the temperature, for example, at a reflux temperature while maintaining an inert gas atmosphere for 8 hours. The compound of the present invention containing a structural unit represented by the formula (8) is a compound having a structural unit represented by the formula (1), and a compound having no structural unit represented by the formula (8) is added with energy, and Y is represented by a divalent group. It can be manufactured by leaving it. When the starting compound has a plurality of divalent groups represented by Y, all of the divalent groups represented by Y may be detached, or one of the groups may be detached. <Solution containing the compound of the present invention and a solvent> The solution of the present invention contains the compound of the present invention and a solvent. In the case of the solvent, examples of the solubility of the compound include an aromatic hydrocarbon solvent, a halogen-substituted aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a crypto-substituted aliphatic hydrocarbon solvent, and an ether solvent. Examples of the aromatic hydrocarbon solvent include, for example, xylene, 1,3,5-trimethylbenzene (mesic), anisole, and cyclohexylbenzene. Examples of halogen-substituted aromatic hydrocarbon solvents include, for example, chlorobenzene, dichlorobenzene, and trichloro 33 323797 201231491 benzene. Examples of aliphatic solvents include, for example, tetralin. Examples of the green-green aliphatic hydrocarbon solvent are listed as four gasified carbon, chloroform, two gas smoldering, one gas sputum, chloroprene sulphur 'dibutin burning, gas smoldering, molybdenum burning, gas burning, The gas ring has burned and the ring has burned. Examples of the ether solvent include tetrahydropyran and tetrahydropyran. When a film containing the compound of the present invention is formed into a film by using a tetraline solution, if the amount of a medium in the liquid is low, the drying step for forming the uniform film may be difficult to control. Therefore, the Buddha's point of the solvent is (10). Preferably, c is above, and above 200 °C is preferred. <Film containing the compound of the present invention> The method for producing the film containing the compound of the present invention is not particularly limited, and a solution containing the compound of the present invention and a solvent is applied to a substrate or the like in view of easiness of film formation. The method is better. The coating method includes, for example, a casting method, a spin coating method, a bar coating method, an inkjet method, a printing method using a relief, and a stencil. The printing method is a method of transferring to the second edition after the first edition is applied, and printing by the second edition. The substrate is not particularly limited, and examples thereof include (4) glass, polyethylene, polystyrene, and gas resin, and films, residual steel, and metal materials, and stone crystal tablets. A film comprising a compound containing a structural unit represented by the formula (8) in the present month is added to a film containing a compound having the structural unit represented by the formula (1) and having a structural unit represented by the formula (8) The energy can be made by removing a part of the divalent base represented by Υ.

34 323797 S 201231491 <Laminate> The laminate of the present invention is a laminate having a matrix and a film, and the film is coated on the substrate with a solution containing the compound of the present invention and a solvent to form a formula (1). The coating film of the compound of the structural unit is further added to the coating film, and the compound (1) contained in at least a part of the entire compound including the structural unit represented by the formula (1) contained in the coating film is contained. A film obtained by converting a structural unit represented by the structural unit represented by the formula (8). When the compound containing the structural unit represented by the formula (1) is added with energy, the divalent group represented by Y in the formula (1) is desorbed to form a compound containing the structural unit represented by the formula (8). Examples of such energy include, for example, thermal energy and light energy. When heat energy is used, any temperature may be set as long as the divalent group represented by the system Y is separated from the temperature of the compound and is lower than the temperature at which the compound is decomposed. It is usually in the range of from 150 ° C to 400 ° C, preferably from 200 ° C to 350 ° C. The time for heat treatment can be selected from the industrial range, usually from 1 minute to 50 hours, preferably from 10 minutes to 24 hours. For a gas atmosphere of heat treatment, an inert gas atmosphere is preferred, such as nitrogen, argon, or vacuum as an example. When oxygen is contained in an inert gas atmosphere, the oxygen concentration is preferably 100 ppm by volume or less, and 10 ppm or less is preferred. Further, when the inert gas atmosphere is a vacuum, the oxygen partial pressure is preferably 200 Pa or less, preferably 50 Pa. A method of illuminating a divalent group represented by Y by light, and irradiating with ultraviolet rays having a wavelength of 400 nm or less is exemplified. The light intensity is not particularly limited as long as the strength of the divalent group represented by Y is removed. Gas at the time of light irradiation 35 323797 201231491 The body is also in an atmosphere of an atmosphere, and the range of the above-described example can be applied. The laminated body of the present invention can be used for an organic transistor, an organic electric field emitting element, or the like. The substrate may be a substrate such as glass or a film, or may have a substrate and an electrode, or may have a substrate, an electrode, and an organic layer. When the laminate is used in an organic transistor, the 'base' is preferably formed by a substrate, a gate electrode, and a gate insulating layer. When the laminate is used for an organic electroluminescent device, the substrate is composed of a substrate, an anode, and an organic layer. The formation is better. The method for producing a laminate of the present invention is a method for producing a laminate having a film and a substrate, wherein a solution containing the compound of the present invention and a solvent is applied onto the substrate to form a structural unit represented by the formula (丨). a step of coating a film of the compound, and adding energy to the coating film, such that the compound represented by the formula (1) contained in at least part of the compound including the structural unit represented by the formula (1) in the coating film 3 The unit is converted into a method for producing a laminate in which the step of forming a thin film is represented by the formula (8). <Organic transistor> The compound of the present invention is suitable for use in an organic semiconductor layer of an organic transistor, and includes an organic electrode layer in which a source electrode and a drain electrode form a current path therebetween. (Active layer), a gate electrode that controls the amount of current passing through the current path, and an electric field effect type organic transistor, an electrostatic induction electron electromechanical crystal, or the like is exemplified. An electric field effect type thin film organic transistor having an organic semiconductor layer (active layer) having a source electrode and a tantalum electrode and forming a current path therebetween, 36 323797

S 201231491 Controls the amount of current passing through this current path. The absolute gate electrode between the semiconductor layer and the gate electrode, and the organic electrode, especially the source electrode and the germanium electrode. The layer is provided, and the organic semiconductor layer is sandwiched between the organic semiconductor layers (the active electrode is preferred. The insulating layer to which the conductor layer is connected is provided with a gate-electrostatic induction type thin organic transistor, / pole, which becomes a current path between the layers) Preferably, the organic semiconductor layer (active layer) having the source electrode and the electric current and controlling the current through the current path is disposed in the organic semiconductor layer. The electrode is disposed between the gate electrode and the gate electrode disposed in the semiconductor layer. The source electrode and the ruthenium electrode are preferably used. Here, the structure of the gate electrode is connected to the organic semiconductor layer as a current path, and it is preferable to apply a structure to the open electrode that the electrode flows to the electrode without forming an electrode. [Examples] Hereinafter, the present invention is not limited to the above, and the present invention is shown in the examples. However, the present example shows that the compound is dissolved in a heavy amount (manufactured by Varian Co., Ltd., IN〇). VA3〇〇), using NMR equipment (number average molecular weight and weight average molecular weight ^ about number average molecular weight and weight average score = permeation chromatography (GPC), find polystyrene The amount of the conversion is determined by the average molecular weight of the gel. The GPC equipment is made of Shimadzu Corporation, molecular weight and weight LC-HJAvp (manufactured by TsKgel SuperHM = product name: U〇S〇H). 323797 37 201231491

1⁄4重量%, Detector: Differential refractive index detector or UV Detector), Waters, trade name: Alliance GPC/V2000C Pipe column: PLgel MIXED-B (Varian) 3 in series, column temperature: 140 ° C, mobile phase: o-diphenyl, flow rate : 1 ml/min, sample concentration: approx. 77 wt%, detector: differential refractive index detector or UV detector). The absorption wavelength of the polymer compound is measured using a spectrophotometer operable in the ultraviolet, visible, and near-infrared wavelength range (for example, a sputum spectroscopic "UV visible near-infrared spectrophotometer JASCO-V670". When JASCO-V670 is used, the wavelength range that can be measured is 200 to 1500 nm, so it is measured in this wavelength range. First, the absorption spectrum of the substrate used for the measurement was measured. As the substrate, a quartz substrate, a glass substrate, or the like is used. Next, a solution containing a polymer compound is applied onto the substrate, and dried to form a film containing the polymer compound. Thereafter, the absorption spectrum of the laminate of the film and the substrate was measured. The difference between the absorption spectrum of the laminate of the film and the substrate and the absorption spectrum of the substrate is the absorption spectrum of the film. Reference Example 1 (Synthesis of Compound (C-2))

38 323797 S 201231491

(C-1)

Addition of compound (Cl) (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.16g (60. 00mmol), maleic anhydride 20.59g (210·Ommol), and toluene 250mL, ventilated at room temperature (25 ° C) with argon gas Soak for 30 minutes. At this time, the compound (C-1) is insoluble to the indolebenzene, and the reaction system is not uniform. The temperature of the oil bath was set to 120 ° C, and the reaction liquid was refluxed for 3.5 hours to carry out a Diels-Alder reaction to make the inside of the reaction system uniform. Thereafter, 20 mL of methanol was added to the reaction liquid for 5 times (100 mL) every 30 minutes, and the mixture was heated to reflux for 3 hours to obtain an acid anhydride ring-opened monoester body. Thereafter, the concentrated sulfuric acid lg was added to the reaction liquid twice a week for 3 hours, and the mixture was heated under reflux for 6 hours. After the solvent in the reaction mixture was removed using an evaporator, 200 mL of hexane was added thereto, and the mixture was stirred at room temperature for 1 hour to remove maleic anhydride. 200 mL of decyl alcohol was added to the reaction liquid, and lg of concentrated sulfuric acid was added twice every 3 hours, and after heating under reflux for 6 hours, the reaction liquid was filtered to remove insoluble matter. Separation of the reaction liquid was carried out using a column using chloroform as a solvent, and the residue was reprecipitated with hexane to obtain a bridge of the colorless powder (compound (C-2)) 25. 17 g. Example 1 39 323797 201231491 (Synthesis of Polymer Compound 1)

(C-2) (A)

In the 100 mL reaction tube in the glove box, the compound (C-2) 311 mg, the bithiophene diborate body (compound (A)) 292 mg, methyltrialkylammonium chloride (methyltrialkylammonium) Chloride) (trade name A1 iquat336 (registered trademark), Aldrich Duo) was weighed and added, and then, in a glove box under nitrogen atmosphere, degassed terpene 12g, degassed potassium carbonate aqueous solution 12g, and catalyst Four (three stupid phosphine) Is (Pd (PPh3) 4) 1.5 mg was added to the reaction tube. The above acid-blocking aqueous solution was prepared by dissolving 282 mg of potassium carbonate in degassed pure water I2g. After the reaction was carried out for 17 hours under reflux conditions, the compound (c-2) was added to the reaction mixture with respect to the compound (c-2), and the odor benzene was added to the reaction liquid to continue reflux for 15 hours, and more, relative to the compound. (C-2) was added to the reaction liquid with an equal amount of 13 moles of phenylboronic acid, and the reaction was stopped after continuing to reflux for 5 hours. After removing the aqueous layer in the reaction mixture, chloroform was added to the organic layer to dissolve the mixture, and the mixture was concentrated by an evaporator and dried under reduced pressure to obtain a crude product. After adding the gas to the obtained crude product and dissolving it by heating, it is subjected to three-stage refining treatment using a column of oxidized and oxidized stone layer, and the solution after the four-column treatment is concentrated by an evaporator, and dried under reduced pressure to obtain a yellow powder. The yield of the polymerized person 1 polymer compound i is · mg. The number average molecular weight of the polystyrene monomer in the polymerized port was 17, (10), and the weight average molecular weight of the polystyrene conversion 323797 40 201231491 was 31,300. Reference Example 2 (Synthesis of Compound (C-3))

For 4-necked flask, add compound (C-2) 4.802 g, bis(pinacolato)diboron 10. 16g and dicrosin 150mL 'Use argon at room temperature (25 ° C) Ventilation was carried out in a 4-neck flask. [1,1'-bis(diphenylphosphino)ferrocene] 1, palladium-bis (diphenylphosphine) ferrocene] dichloro palladium (II) 408. 3 mg, 1,1' _ double (Diphenylphosphine) ferrocene 277. 2 and potassium acetate 3. After the addition of 926 g, the reaction solution was heated to reflux for 7 hours. After the reaction, the raw materials disappeared by liquid chromatography. The reaction was carried out under an argon atmosphere. The insoluble base in the reaction liquid is separated by a crucible. The reaction solution was dried by an evaporator for 30 minutes to remove the solvent. In the same manner as in Reference Example 1, the reaction solution was separated by a column, and the isolate was dissolved in a small amount of acetone, and a mixture of sterol was added thereto to obtain a bis(pinacol) ester of the compound (c_2) by adding a small amount of water. (Compound (C-3)) 3·50g. The yield of the compound (〇3) was 60.9 %, and the area fraction obtained by liquid chromatography was 97 % by purity. The 1h-NMR (CDzCl2 (ppm)) shift values of the obtained compound (C-3) are shown as (s, 24H), 3.17 (m, 2H), 3.48 (d, 6H), 4.58 (s, 2H), 7. 28 (m, 2H), 7.50 (m, 2H), 7.67 (s, 2H), confirm the target 323797 41 201231491. Example 2 (Synthesis of Polymer Compound 2)

In a 50 mL three-necked flask, 230 mg of the compound (C-3), 184 mg of the triphenylamine derivative (compound (B)), and vaporized mercaptotrialkylammonium (trade name: Aliquat 336 (registered trademark), manufactured by Aldrich Co., Ltd.) were weighed in an amount of 81 mg. After the addition, 12 mL of degassed terpene was added under an argon atmosphere, and the temperature was raised to 90 °C. Next, I bar diacetate (Pd (OAc) 2) 0.92 mg and tris(o-nonyloxyphenyl)phosphine (P ( 〇-MeOPh) 3) 34. 95 mg were added to the reaction solution, and the temperature was raised to 100 °. After C, a degassed 16.7% sodium carbonate (Na2C〇3) aqueous solution was dropped at 2.54 g. Thereafter, after a half reaction for 5 hours and 27 minutes at 10 ° C, the compound (C-3) 4.59 mg, 0.95 mg Pd (OAc) 2, 4.95 mg P ( ο-MeOPh ) 3 was dissolved in 4 mL of toluene was added to the reaction solution. Thereafter, the reaction was carried out at 100 ° C for 2 hours and 10 minutes. After standing to cool to room temperature, the oil layer of the reaction mixture was washed with water for 2 times, washed with a 3% aqueous solution of acetic acid for 1 time, washed with water for 3 times, and dried over sodium sulfate (Na 2 S 4 ). Thereafter, the column was purified using a column of alumina and yttria, and the solution treated by the column was concentrated, and the concentrate was added to methanol to collect a precipitate, which was dried to obtain a polymer compound 2. The yield of the polymer compound 2 was 133 mg. High score 42 323797

S 201231491 = weight of two, the converted number average molecular weight is the weight average molecular weight of the polyethylene conversion is 14, 〇〇〇. Example 3 ‘° (Production of Film) This was adjusted to contain 0.5 Å of a ruthenium wafer and a glass. The polymer compound 1 was dissolved in chloroform, and the chloroform solution of the compound 1 was transferred to a film to obtain a film. Example 4 (Manufacture of laminate)

The film on the Shi Xi wafer and the film on the glass were heat-treated at 300 ° C in a nitrogen atmosphere to produce a laminate. Regarding the film formed on the ruthenium wafer, the infrared absorption spectrum of the film before and after the heat treatment was measured by an infrared spectrophotometer. The infrared absorption spectrum of the film before the heat treatment and the infrared absorption spectrum 12 of the film after the heat treatment are shown in Fig. 1. Further, the ultraviolet visible absorption spectrum of the film before and after the heat treatment of the film formed on the glass was measured by an ultraviolet-visible spectrophotometer. The ultraviolet visible absorption spectrum 21 of the film before the heat treatment and the ultraviolet visible absorption spectrum 22 of the film after the heat treatment are shown in Fig. 2. By the heating of the film, the peak of the thin film vinegar structure disappears in the infrared absorption light 323797 43 201231491 1750 cm_1. Further, by heating of the film, a peak of 540 nm derived from the ultraviolet visible absorption spectrum of the conjugated system expansion is generated. The knots are shown in Table 1. [Table 1] Infrared absorption spectrum of the film on the yttrium wafer The ultraviolet visible absorption spectrum of the film on the peak glass of ΠδΟαιΓ1 has a peak without peaks before heating at 540 nm. There is no peak after peak heating. Reference Example 3 (Organic transistor (Production) Using the polymer compound 1, an organic thin film transistor having the structure shown in Fig. 3 was produced by the following method. First, the surface of the 11-type germanium substrate 31 which is doped with a high concentration of the gate electrode is thermally oxidized to form a tantalum oxide film 32 of a ship. The fire is etched by the light meal method. (photolithography) on the crushed ruthenium oxide 32, a channel length of 20 μm, a channel width of the source electrode 33, and a germanium electrode 34 (formed by a film laminated in the order of chromium and gold from the tantalum oxide film side) is obtained. After the substrate is sufficiently washed, the surface of the substrate is subjected to a smelting treatment by using a hexamethylene difluoride, a HMDS, and a U-turn coating. Next, the polymer compound is dissolved in the gas imitation. Prepare a mass% of the solution and filter it with a lining. The solution after the transition is applied to the surface-treated substrate by spin coating. Thereafter, under a nitrogen atmosphere of 323797 44 201231491 The heat treatment was performed at 300 ° C for 1 hour to form an organic semiconductor layer 35. (Measurement of transistor characteristics) For the fabricated organic thin film transistor, the gate voltage Vg was 10 to 60 V, and the source/turn voltage Vsd was -6 〇V. Determine the characteristics of the transistor, and calculate the characteristics of the measurement. The electric field effect mobility was 5 x 10 × 3 cm 2 /Vs. The results are shown in Table 2. Reference Example 4 (Production of Organic Electrode) Using the polymer compound 2, an organic thin film transistor having the structure shown in Fig. 4 was produced by the following method. First, the surface of the n-type fracture substrate 31 which is a high-density mixed gate electrode is thermally oxidized to form a crushed oxide film 32 of 1 〇〇nijj. After the substrate thus obtained is sufficiently washed, the simmering coupling agent is used. The surface of the substrate was subjected to decane treatment with octadecyltrichlorosilane. Secondly, a polymer compound 2 was dissolved in chloroform to prepare a 0.5% by mass solution, and this solution was spin-coated on the surface-treated substrate. Thereafter, the film was heat-treated at 300 C for 1 hour in a nitrogen atmosphere to form an organic semiconductor layer 35. Second, a channel length of 20/zm was formed on the organic semiconductor layer 35 by a resistance heating evaporation step. The source electrode 33 and the ytterbium electrode 34 of the wide position (formed by a film laminated in the order of Mo 〇 3 and gold from the side of the organic semiconductor layer) (measurement of the characteristics of the transistor) The organic thin film transistor has a transistor characteristic measured at a gate voltage Vg of 1 〇 to 60 V and a source/turn voltage Vsd of -6 〇 v. The electric field effect mobility obtained by the measured characteristic is 2 4 χ 1 〇_4 323797 45 201231491 cm2/Vs. The results are shown in Table 2. Example 5 (Synthesis of Polymer Compound 3)

Into a 200 ml 4-necked flask, Compound (D) 392. 2 mg, Compound (C-2) 480. 2 mg, and tetrahydrofuran 20 mL were added, and argon gas was bubbled at room temperature (25 ° C) for 30 minutes. Next, 18.31 mg of tris(tert-butyl) phosphonium tetrafluoroborate (23 mg) of tris(dibenzylideneacetone) was added to the reaction liquid. While stirring the reaction solution at room temperature, 2 g of a 27.6% by weight aqueous potassium carbonate solution was added dropwise over 30 minutes, and the temperature was raised to 50 °C. After 10 minutes, the temperature was raised to 80 ° C and refluxed for 3 hours. The obtained reaction liquid is treated with an aqueous solution of sodium N,N-diethyldithicarbamate (Sodium N,N-diethyldithi〇carbamate), which is heated to form a soluble portion, passed through alumina and oxidized. Tube 杈 0 is dry, high purity is obtained, and the polymer compound is filtered. The obtained polymer compound was washed * ^ 1 ' The liquid treated in the column was added to methanol to recover the precipitate, and the molecular compound 3 was obtained. The yield of the polymer compound 3 is a polystyrene-equivalent number average molecular weight of the compound 3. The weight average molecular weight of the polymer in terms of ethylene is 42,4 Å. Π, 500, 聚笨 Reference Example 5 323797 46 201231491 (Production of Organic Electrode) Using the polymer compound 3, an organic thin film transistor having the structure shown in Fig. 4 was produced by the following method. First, the surface of the high-concentration doped n-type crystal substrate 31, which is a gate electrode, is thermally oxidized to form a 10 angstrom oxide film 32. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to decane treatment using a decane coupling agent, octadecyltrichloromethane. 5质量百分比的溶液。 Next, the high molecular compound 3 was dissolved in chloroform to prepare a 0.5% by mass solution. This solution was heated to 50 ° C and coated on the above-mentioned surface-treated substrate heated at 50 ° C by a spin coating method. Thereafter, heat treatment was performed at 300 ° C for 1 hour in a nitrogen atmosphere to form an organic semiconductor layer 35. Next, a source electrode 33 having a channel length of 20//in, a channel width of 2 Å, and an electrode 34 are formed on the organic semiconductor layer 35 by a resistance heating evaporation step (from the side of the organic semiconductor layer, Mo 〇 3, Gold is formed by a film of sequential layers). (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 10 to 60 V and a source/turn voltage Vsd of 60 V. The electric field effect mobility obtained by the measured characteristic is 7. Ox 10 -3 cm2 / Vs. The results are shown in Table 2. Example 6 (Synthesis of Polymer Compound 4) 47 323797 201231491

ο

Polymer compound 4 was synthesized in the same manner as in Example 2 except that the compound (Ε) was used instead of the compound (Β). The yield of the polymer compound 4 was 35 mg. Reference Example 6 (Production of organic transistor) An organic transistor having a structure shown in Fig. 4 was produced by the following method using the molecular compound 4'. First, the surface of the η-type slab substrate 31, which is a high concentration of the gate electrode, is thermally oxidized to form a bismuth oxide 32 at 1 〇〇 nm. Next, the polymer compound 4 was dissolved in o-dioxane to prepare a solution of ^ 2 % by volume. This solution was heated to 14 passages and applied by spin coating to the above substrate which had been heated to un:. Thereafter, heat treatment was carried out for 1 hour in a nitrogen atmosphere to form an organic semiconductor layer 35. Next, on the organic semiconductor layer 35, a source electrode 33 having a channel length m and a channel width of 2 mm and a material electrode % (made by a semiconductor semiconductor, Mq 〇 3, and a gold accumulation layer) are formed by a resistance heating and smelting step. 323797 48 201231491 (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 1 〇 to -60 V and a source/turn voltage Vsd of 60 V. The electric field effect mobility obtained from the measured characteristics is ΐ 2χ1〇_3 cm2/Vs. The results are shown in Table 2. Example 7 (Synthesis of Polymer Compound 5)

(C-3) (F)

Polymer compound 5 was synthesized in the same manner as in Example 2 except that the compound (F) was used instead of the compound (B). The yield of the polymer compound 5 was 190 mg. The number average molecular molecule 1 of the polymer compound 5 in terms of polystyrene was 60,000, and the weight average molecular weight in terms of polystyrene was 94, 〇〇〇. Reference Example 7 (Production of organic transistor) An organic transistor having the structure shown in Fig. 4 was produced by the following method using the polymer compound 5'. First, the surface of the high-density doped n-type slab substrate 31 is thermally oxidized to form a bismuth film of 323 nm 323797 49 201231491 32. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to decane treatment using a decane coupling agent octadecyltrichloromethane. 5质量百分比的溶液。 Next, the polymer compound 5 was dissolved in a gas sample to prepare a solution of 0.5% by mass. This solution was applied onto the above-mentioned surface-treated substrate by spin coating. Thereafter, heat treatment was performed at 300 ° C for 1 hour in a nitrogen atmosphere to form an organic semiconductor layer 35. Next, a source electrode 33 having a channel length of 20/zm and a channel width of 2 mm and a non-electrode 34 are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition step (from the side of the organic semiconductor layer, in the order of Mo〇3, gold) The film is formed). (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 1 Torr to -60 V and a source/turn-to-turn voltage vsd of 60V. The electric field effect mobility obtained from the measured characteristics is 7.5 - 4 cm /Vs. The results are shown in Table 2. Example 8

(Synthesis of Polymer Compound 6) Μα Μβ CioHoK

50 323797 s 201231491 The polymer compound 6 was synthesized in the same manner as in Example 2 except that the compound (G) was used instead of the compound (β). The yield of the polymer compound 6 was 100 mg. The polymer compound 6 has a polystyrene-equivalent number average molecular weight of 20,000 Å. The polystyrene-equivalent weight average molecular weight is 28, (10) 〇 ^ Reference Example 8 ' (Production of an organic transistor) Using a polymer compound 6, the following The column method produces an organic transistor having a structure not shown in Fig. 4. First, the surface of the n-type slab substrate 31 doped with a high concentration of the gate electrode is thermally oxidized to form a iridium oxide film 32 of i 〇〇 nm. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to a heat treatment using a decane coupling agent phenethyl trichlorosilane. Next, the polymer compound ? was dissolved in toluene to prepare a 0.5 mass% solution. This solution was heated at 1 Torr (rc) by spin coating on the above surface-treated substrate heated by i〇〇c. Thereafter, it was carried out at 3 ° C under a nitrogen atmosphere. After heat treatment for 1 hour, the organic semiconductor layer 35 is formed. Next, a source electrode 33 having a channel length of 20/zm and a channel width of 2 mm and a germanium electrode 34 are formed on the organic semiconductor layer 35 by a resistance heating evaporation step (from the side of the organic semiconductor layer) It is formed by a film laminated in the order of M〇〇3 and gold. (Measurement of transistor characteristics) For the fabricated organic thin film transistor, the gate voltage Vg is 1 〇 to 60 V, and the source/turn voltage Vsd is The transistor characteristics were measured at ~6 〇v. The electric field effect mobility calculated from the measured characteristics was ΐ 8 χΐ〇 2 cm 2 /Vs. The results are shown in Table 2. 323797 51 201231491 Example 9 Synthesis of Polymer Compound 7 )

Polymer compound 7 was synthesized in the same manner as in Example 2 except that the compound (H) was used instead of the compound (B). The yield of the polymer compound 7 was 74 mg. The polymer compound 7 had a polystyrene-equivalent number average molecular weight of 5.9 000 and a polystyrene-equivalent weight average molecular weight of 890,000. Reference Example 9 (Production of organic transistor) Using the polymer compound 7, an organic transistor having the structure shown in Fig. 4 was produced by the following method. First, the surface of the η-type slab substrate 31 which is doped with a high concentration of the gate electrode is thermally oxidized to form a 100 nm oxidized film 32. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to decane treatment using a decane coupling agent phenethyltrichloromethane. 5质量百分比的溶液。 Next, the polymer compound 7 was dissolved in benzene to prepare a solution of 0.5% by mass. This solution

52 323797 S 201231491 is coated on the above-mentioned surface-treated substrate by spin coating. Thereafter, under the nitrogen atmosphere, heat treatment was performed for 27 hours at TC to form the organic semiconductor layer 35. Secondly, a channel length of 2 〇βιη and a channel width of 2 mm were formed on the organic semiconductor layer 35 by a resistance heating distillation step. The electrode 33 and the electrode 34 (formed by a film laminated in the order of M〇〇3 and gold from the side of the organic semiconductor layer). 曰 (Measurement of transistor characteristics) For the fabricated organic thin film transistor, at the gate voltage The Vg is 10 to -60 V, and the source/turn-to-turn voltage vsd is measured at -60 V. The electric field effect mobility calculated from the measured characteristics is 3. 3 χ 1 〇 -3 cra2 / Vs. The results are shown in Table 2. Example 1 〇 (synthesis of polymer compound 8)

Polymer compound 8 was synthesized in the same manner as in Example 1 of 53 323 797 201231491 except that the compound (C-4) was used instead of the compound (C-2). The yield of the polymer compound 8 was 100 mg. Reference Example 10 (Production of organic transistor) Using the polymer compound 8, an organic transistor having the structure shown in Fig. 4 was produced by the following method. First, the surface of the n-type slab substrate 31 which is doped with a high concentration of the gate electrode is thermally oxidized to form a 10 Å SiO film 32. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to decane treatment using a decane coupling agent phenethyltrichloromethane. 5质量百分比的溶液。 Next, the polymer compound 8 was dissolved in chloroform to prepare a 0.5% by mass solution. This solution was applied onto the above-mentioned surface-treated substrate by spin coating. Thereafter, heat treatment was performed at 300 ° C for 30 minutes in a nitrogen atmosphere to form an organic semiconductor layer 35. Next, a source electrode 33 having a channel length of 20/zm, a channel width of 2 Å, and a germanium electrode 34 are formed on the organic semiconductor layer 35 by a resistance heating evaporation step (from the side of the organic semiconductor layer, in the order of Mo〇3, gold) The film formed by the layer). (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 10 to 60 V and a source/turn voltage Vsd of 60 V. The electric field effect mobility obtained from the measured characteristics is 4.8xl0~2 cm2/Vs. The results are shown in Table 2. Example 11 (Synthesis of Polymer Compound 9)

54 323797 S

[123⁄4 201231491

(C-3)

〇12Η25

(J)

The compound (1) is used instead of the compound ( : the polymer compound 9 is synthesized in the same manner. The high-two and the embodiment are the polymer compound 9 poly-complex: the yield is the weight average of the polystyrene lion; = equal reference Example 11 The knife is 82,000 (manufactured by organic transistor)

-^ The electrophoretic crystal having the 4th I type II was produced by the following method using the fluorene molecular compound 9'. First, the high concentration of the gate electrode is made 32. After the substrate such as ruthenium is thermally oxidized to form a substrate of 1 〇〇 nm, the substrate obtained by trichloromethane is sufficiently washed, and then the surface of the substrate is subjected to decane treatment using a money coupling agent. Second, the high score is turned into. The substance Q is dissolved in the gas to make the winter... By rotating the Blessing ".5% of the stock solution. This dissolution-coating method was applied to the above-mentioned surface-treated, and was subjected to a nitrogen atmosphere at 25 Torr. Rebellious machine semi-guided _ 35. (4) Treating 1 cut, forming a source electrode 33 having a channel length of 2 Å, a channel width of 2 mm, and a ytterbium electrode 34 (from the organic semiconductor layer) by a resistive heating evaporation step on the organic semiconductor 323797 55 201231491 The side is formed by a film laminated in the order of m〇〇3 and gold). (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 1 Torr to -60 V and a source/turn voltage vsd of -6 〇v. The electric field effect mobility obtained from the measured characteristics is 13χ1〇-3 cm /Vs. The results are shown in Table 2. Example 12 (Synthesis of Polymer Compound 10)

The polymer compound 10 was synthesized in the same manner as in Example 2 except that the compound (K) was used instead of the compound (B). The yield of the polymer compound 1 〇 was 133 mg. The polymer compound 1 〇 has a number average molecular enthalpy of 54 000 in terms of polystyrene, and a weight average molecular weight of 90,000 in terms of polystyrene. Reference Example 12 (Production of Organic Crystal) Using a polymer compound 1 〇, An organic transistor having the structure shown in Fig. 4 was produced in the following manner. The surface of the high-intensity doped n-type germanium substrate 31, which is a gate electrode, is thermally oxidized to form a germanium oxide film of 1 〇〇 nm 323797 56 201231491 32. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to a calcination treatment using a decane coupling agent styrene trichloromethane. 5质量百分比的溶液。 Next, the polymer compound 10 was dissolved in chloroform to prepare a solution of 0.5% by mass. This solution was applied onto the above-mentioned surface-treated substrate by spin coating. Thereafter, heat treatment was performed at 330 ° C for 1 hour in a nitrogen atmosphere to form an organic semiconductor layer 35. Next, a source electrode 33 having a channel length of 20# m and a channel width of 2 mm and a germanium electrode 34 are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition step (from the side of the organic semiconductor layer, in the order of Mo〇3, gold) The film is formed). (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 10 to 60 V and a source/turn voltage Vsd of 60 V. The electric field effect mobility calculated from the measured characteristics was 4. 8 x 1 (T 3 cm 2 /Vs. The results are shown in Table 2. Example 13 (Synthesis of Polymer Compound 11)

The polymer compound 11 was synthesized in the same manner as in Example 2 except that the compound (L) was used instead of the compound (B). The yield of the polymer compound 11 was 145 mg. The polymer compound 11 had a polystyrene-equivalent number average molecular weight of 25,000 and a polystyrene-equivalent weight average molecular weight of 57 323797 201231491 41,000. Reference Example 13 (Production of organic transistor) Using the polymer compound 11, an organic transistor having the structure shown in Fig. 4 was produced by the following method. First, the surface of the η-type slab substrate 31 which is doped with a high concentration of the gate electrode is thermally oxidized to form a 100 nm oxidized film 32. After the substrate thus obtained was sufficiently washed, the surface of the substrate was subjected to decane treatment using a decane coupling agent phenethyltrichloromethane. 5质量%的溶液。 Next, the polymer compound 11 was dissolved in chloroform to prepare a 0.5% by mass solution. This solution was applied onto the above-mentioned surface-treated substrate by spin coating. Thereafter, heat treatment was performed at 300 ° C for 1 hour in a nitrogen atmosphere to form an organic semiconductor layer 35. Next, a source electrode 33 having a channel length of 20 μm and a channel width of 2 mm and a germanium electrode 34 are formed on the organic semiconductor layer 35 by a resistance heating vapor deposition step (from the side of the organic semiconductor layer, in the order of Mo 3 and gold) Formed by the film). (Measurement of transistor characteristics) For the produced organic thin film transistor, the transistor characteristics were measured at a gate voltage Vg of 10 to 60 V and a source/turn voltage Vsd of 60 V. The electric field effect mobility obtained from the measured characteristics was 2.9 xl (T 4 cm 2 /Vs. The results are shown in Table 2. 58 323797

S 201231491 & [Table 2] Electric field effect mobility (cm2/Vs) of polymer compound Reference example 3 Polymer compound 1 5xl03 Reference Example 4 Polymer compound 2 2.4xl0-4 Reference example 5 Polymer compound 3 7·0χ1 ( Γ3 Reference Example 6 Polymer Compound 4 1. 2χ10'3 Reference Example 7 Polymer Compound 5 7. 5χ10'4 Reference Example 8 Polymer Compound 6 1. 8χ10-2 Reference Example 9 Polymer Compound 7 3. 3χ10-3 Reference Example 10 Polymer Compound 8 4. 8χ10-2 Reference Example 11 Polymer Compound 9 1. 3χ10'3 Reference Example 12 Polymer Compound 10 4. 8χ10'3 Reference Example 13 Polymer Compound 11 2. 9χ10-4 [Pattern BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an infrared absorption spectrum before and after heating of a film of Example 3. Fig. 2 is an ultraviolet visible light absorption spectrum before and after heating of the film of Example 3. Fig. 3 is an organic transistor manufactured by Reference Example 3. Cross-sectional view of the structure. Fig. 4 is a cross-sectional view showing the organic transistor structure manufactured by Reference Examples 4 to 11 59 323797 201231491. [Explanation of main components] 11 Infrared absorption spectrum of the film before heat treatment 12 After heat treatment Drain electrode 34 of the infrared absorption spectrum of the thin film 21 the film is heated prior to the ultraviolet visible absorption spectrum of the treated film 22 is heated after the UV-visible absorption spectrum of the process 33 of the source electrode 32 of silicon oxide film 31 n- type silicon substrate 35 of the organic semiconductor layer

Claims (1)

201231491; VII. Patent application scope: 1. A compound having: a structural unit represented by formula (1) (1) wherein R and R are each independently and represent a substituent, and r3 and fluorene are each independently represented by a hydrogen atom or a substituent, and π and m are each independently, and represent an integer of 0 to 3, and γ represents a valence group, R1 is plural, and the like may be the same or different, and when R2 is plural, the structures may be the same as those represented by the formula (2), (3) or (4). unit [In the formulae (2) to (4), y main-t 貉 貉 - n R is unsubstituted, S represents i grass integer, ρ is not an integer of 4, q 李八1 to 4 is a plural In this case, the f can be the same or the number of H, G to 4, and R5 is the structural unit represented by the formula (5) 201231491 (5) [wherein, Ar1 represents a C C C-, a c (ra) = c (rA) -, - N = N -, - C (RB) = N -, may have a substituent ring carbon number 8 The above-mentioned aryl group or a heteroaryl group which may have a substituent, but A〆 is not a group represented by the above formula (1), and two Ra are each independently a hydrogen atom or a substituent, and RB represents a hydrogen atom. Or a substituent] and a structural unit represented by the following formula Ar2-N-|-Ar3—N^—Ar4 hr5 Ar6 [wherein, r and rr represent the number of structural units (_Ar3—NAr6—) and the number of structural units (“Ar5—NAr7—), respectively, which are independent, 0 or Ar, Ar3, Ar4, and Ar5, each independently. a heteroaryl group which may have a substituent or a heteroaryl group which may have a substituent, Ar, Ar and Ar8, each independently, representing an aryl group which may have a substituent or a heteroaryl group which may have a substituent A group of compounds selected from at least one structural unit. 2. The compound according to claim 1, wherein the compound has two or more structural units represented by the formula (1). 3. If the compound mentioned in the second or second paragraph of the patent application is applied, the repacking 2 323797 201231491 includes eight or more structural units represented by the formula (7) The compound of the valence group according to any one of the items 3 to 3, which is represented by the formula (丫~丨) to (γ4, as represented by the first item in the patent application, wherein Y is represented by 8). _[ί (Υ-υ to (γ-8), R*° to R2°, each independently, a table-atom or a substituent 'X, representing a hydrogen atom or a self-atomic atom, when the heart is plural, such Can be the same or different] At least one basis selected by the group. The compound according to any one of claims 1 to 4, wherein the compound having a weight average molecular weight of 3 Å or more is a polymer compound. The compound as described in any one of claims 1 to 5 has a structural unit represented by the formula (8). 323797 3 (8) 201231491 [wherein, 〇, 111, 1^, 1^, 1^ and R4 represent the same meaning as in the formula (1)]. A solution comprising a compound according to any one of claims 6 to 6, and a solvent. A film comprising a compound according to any one of claims 6 to 6. 9. A laminate comprising a substrate and a film, wherein the film is coated on the substrate to form a coating film containing a compound containing a structural unit represented by the formula (丨), and secondly Adding energy to the coating film to convert the structural unit represented by the formula (1) contained in at least a part of the entire compound containing the structural unit represented by the formula (j) into the formula (8) a film obtained by expressing the structural unit. 10. A method for producing a laminate comprising a film and a substrate, comprising the steps of: applying a solution according to claim 7 of the patent application to a substrate to form a compound containing a structural unit represented by the formula (1) a step of coating the film, and adding energy to the coating film, the structural unit represented by the formula (1) containing at least a part of the entire compound containing the structural unit represented by the formula (1) The step of forming a film by converting into a structural unit represented by the formula (8). 4 323797