TW201002762A - Underlayer film composition for forming image - Google Patents

Abstract

A composition for forming an underlayer film for image formation is provided which gives an image-forming underlayer film having high water repellency (hydrophobicity), capable of being easily changed in hydrophilicity/hydrophobicity by exposure even to a small amount of ultraviolet, and having a high relative permittivity. Also provided is a cured film obtained from the composition. The composition for forming an underlayer film for image formation is characterized by containing at least one member selected from the group consisting of a polyimide precursor comprising structural units represented by the following formulae (1) and (1a) and a polyimide obtained by the dehydrating cyclization of the polyimide precursor. (In the formulae, A represents a tetravalent organic group; B1 represents a divalent organic group having fluoroalkyl; B2 represents a divalent organic group; R1, R2, R1a, and R2a each independently represents hydrogen or a monovalent organic group; and n and m each is a positive integer, provided that 0.01≤n/(n+m)≤0.3.)

Description

201002762 VI. Description of the Invention: [Technical Field] The present invention relates to image formation of a polyimide containing a polyimide precursor and/or a polyimine obtained by subjecting the polyimide precursor to dehydration ring closure The underlayer film composition is further related to a cured film and an electronic device produced using the composition. [Prior Art] In the manufacturing process of an electronic device, a pattern of an electrode or a functional film is formed, and a coating technique using a difference in wettability of a liquid is applied to the patterning of a functional film. This is a pattern layer formed on the surface of the substrate to form a region where the liquid is easily wetted and a region where the liquid is not easily wetted, and then the liquid containing the functional film forming material is continuously applied to the pattern layer and dried, only for the liquid. A method of forming an electronic device such as an organic EL (electroluminescence) device or an organic FEI (electric field effect transistor) device by forming a functional film in a region that is easy to wet. The image forming liquid used in the formation of the electrode pattern described above is mainly composed of a PEDOT/PSS aqueous solution. However, the surface tension of the PEDOT/PSS aqueous solution is high, so that it is difficult to form a film by a spin coating method or a printing method. Therefore, it is generally adjusted to a lower surface tension. Since the image forming liquid having a low surface tension exhibits the property of spreading the wetness of the substrate to be formed into a film, it is necessary to make the target portion hydrophilic only in order to suppress the liquid wet expansion in the region other than the target portion. The surface of the region is hydrophobic -5 - 201002762 In recent years, a patterned layer such as an electrode or a functional film can be used by a polyimide precursor containing a hydrophobic side chain or by a polyimide precursor. The obtained polyimine has a change in the water contact angle by changing the hydrophilicity of the ruthenium imine film, and the technique of coating the coated functional material has been extensively studied. For example, the property of the wetness-changing layer obtained by using a polyfluorene imine precursor having an aliphatic ring or polyimine has been clearly shown (for example, refer to Patent Document 1). In this document, it is presumed that one of the factors causing the change of the hydrophilicity and hydrophobicity of the aliphatic ring of the polyimine is also caused by the fact that the amount of the side chain (that is, the number of side chains) is large, and the surface energy (critical surface) The tension) becomes low and becomes lyophobic. In the examples of the same literature, it is disclosed that when a polyamic acid obtained by using a dicarboxylic acid having an aliphatic ring and a diamine having a hydrocarbon group in a side chain is used as a wetness change layer, it is revealed that the hydrophilicity and hydrophobicity are greater by ultraviolet irradiation. As a result of the change, an electrode layer composed of PEDOT/PSS was formed on the wetness-changing layer to fabricate an electronic component. [Patent Document 1] International Publication No. 2006/137366 [Disclosure] [Problems to be Solved by the Invention] Generally, in order to form an image forming liquid, it is possible to have a surface tension lower than that of water. For this reason, the image forming liquid is often considered to have an organic solvent system having a surface tension lower than that of water. However, in the hydrophobic side chain exemplified in the above literature, even if the side chain contains a considerable amount of -6 201002762, the hydrophobicity (ie, water repellency) of the unexposed portion cannot be said to be sufficiently high in the stomach, for example, exudation in the unexposed portion. When the image forming liquid is formed, the final image is dried by a large amount of liquid, and there is a problem that the desired image cannot be obtained. Furthermore, the hydrophobic group is generally lower than the dielectric constant, and the increase in the side chain content causes a decrease in the specific dielectric ratio, especially the fluoroalkyl group having a higher hydrophobicity, and the specific dielectric ratio is also higher than that of other hydrophobic groups. It is extremely low, so it cannot be said that it is preferable in the gate insulating film used in an organic transistor or the like. There is a problem. Therefore, the image forming underlayer film which is mainly used for the patterning of the source and the gate electrode of the organic transistor needs to have the function as a gate insulating film at the same time, so that it is not used in the side chain. A polyfluoroimine-based material of a fluoroalkyl group is exemplified as an underlayer film for image formation. Therefore, the material is designed in such a manner that the specific gate insulating film is lowered in order to lower the driving voltage of the organic transistor, or the fluorine-containing alkyl group is added as much as possible for the purpose of improving water repellency (hydrophobicity). The content of the side chain, even if the specific dielectric ratio is drastically lowered, for example, by patterning a fine image by high water repellency, there is still a problem that the performance of the gate insulating film is lowered. Therefore, there is a demand for a novel material having a hydrophobic side chain which can suppress a decrease in dielectric ratio while achieving high water repellency. The present invention has been made in view of the above circumstances, and an object thereof is to provide an underlayer film composition for image formation, which has an image forming underlayer film having high water repellency (hydrophobicity) and a small amount of ultraviolet light exposure. The hydrophilicity and hydrophobicity can be easily changed, and the decrease in specific dielectric ratio can be suppressed. Further, an object of the present invention is to provide an underlayer film composition for image formation, which is formed by an image forming liquid having a low surface tension solvent 201002762 as a main solvent by a coating method such as a spin coating method or an inkjet printing method. 'High-resolution map (image formation). In addition, the present invention provides an underlayer film forming composition and an excellent insulating property which can be fired at a temperature of 200 ° C or lower (1 80 ° C or lower) and has high electrical insulating properties or chemical stability. A gate insulating film for an organic transistor having a good characteristic of low leakage current. [Means for Solving the Problem] The inventors of the present invention have found that the polyimine imine and/or the polyimine obtained from the polyimide precursor are obtained by repeating the positive review for the above purpose. In the obtained polyimine structure, a phenyl group having a fluoroalkyl group is introduced in a range of not more than 30 mol%, and not only a change in hydrophilicity/hydrophobicity but also a high dialing can be imparted by irradiation of ultraviolet rays. The present invention has been completed by water-based without lowering the specific dielectric ratio. That is, the first object of the present invention relates to an underlayer film composition for image formation characterized by containing a polyimine precursor having a structural unit represented by the following formulas (1) and (la) and At least one compound selected from the group consisting of polyazonia imines obtained by dehydration ring closure of the polyamidene precursor:

/R1aOOC C00R28 \ L \ ΐΐ ΤΓΐ 201002762 (wherein A represents a tetravalent organic group, B1 represents at least one divalent organic group represented by the following $(2), and B2 represents a divalent organic group, RI, R > R1 ' R2a independently represents a hydrogen atom or a monovalent organic group, and η is the total number of moles of the structural unit represented by the formula (1) 'm is the total number of moles of the structural unit represented by the formula (la), and η and m respectively represent A positive integer satisfies 〇.〇ign/(n + mpQ 3) [Chemical 2] 々Xl, xrR3 (2) (wherein, X] represents a single bond, _〇-, -COO-, -OCO-, -CONH -, -CH20-, X2 represents a divalent organic group having 3 to 18 carbon atoms, and R3 represents a perfluoroalkyl group having 2 to 12 carbon atoms. The second object of the present invention is an image relating to the above first object. The underlayer film composition for forming, wherein in the above formula (1), B2 is at least one selected from the group consisting of the following formulas (3) to (5): [Chemical 3]

(wherein Y1 independently represents a single bond, an ether bond, an ester bond, a sulfuric acid bond-9 - 201002762, a guanamine bond, an alkyl group having a branched structure of 1 to 3 carbon atoms, or a carbon number of 1 to 3 may have a branched structure of alkylene oxide, γ represents a single bond, an ether bond, an ester bond, a thioether bond, a guanamine bond, and R respectively represents a hydrogen atom, a methyl group, a trifluoromethyl group, and R5 represents A hydrogen atom, a methyl group, a difluoromethyl group, and R6 represents a methyl group and an ethyl group, and j is independently represented by hydrazine or hydrazine. The third object is the underlayer film composition for image formation according to the above first object or the first object, wherein the tetravalent organic group represented by 'A in the above formula (1) and formula (la) is At least one species selected from the group consisting of the following formulas (6) to (1 1}

(wherein, r7, R8, R9, and R1Q each independently represent a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 4 carbon atoms). As a fourth object, it is related to any one of the above first to third objects. The underlayer film composition for image formation described above contains a polyimine precursor having a structural unit represented by the above formulas (1) and (la), and a polyfluorene obtained by dehydration ring closure of the polyimine precursor. The sub-ammonium is a polyimine precursor and a polyaniline obtained by reacting a tetracarboxylic dianhydride represented by the following formula (16) with a diamine component represented by the following formulas (17) and (18): -10- 201002762 [化5]

(1β) (17)

HaN-B^Ha (18) (wherein, A, B1 and B2 are the same as defined in the above formulas (1) and (la)). The fifth object of the present invention is to use the underlayer film for image formation obtained by using the underlayer film composition for image formation according to any one of the first object to the fourth object, and to use the first object to the fifth object. The underlayer film for electrode pattern formation obtained by the underlayer film composition for image formation described in any of the above. The seventh object is the gate insulating film for an organic transistor obtained by using the underlayer film composition for image formation described in any of the first to fifth aspects. The eighth object is an organic transistor obtained by using a gate insulating film for an organic transistor described in the seventh object. [Effect of the Invention] The underlayer film composition for image formation containing at least one compound selected from the group consisting of a polyimide intermediate and a polyimine obtained from the polyimide precursor is used. The film formed therefrom can be made to change the hydrophilicity of the film by changing the contact angle of the image forming liquid which is used as a main solvent with a solvent having a low surface tension by irradiation with ultraviolet rays. -11 - 201002762 By using these characteristics, an underlayer film can be formed which can form an image of a functional material such as an electrode. Further, the cured film formed of the composition of the present invention can form an underlayer film for image formation of a dielectric ratio cylinder. The underlayer film for image formation which is more than a dielectric property can also be used as a gate insulating film for an organic transistor. Further, the underlayer film for image formation having a high electric current rate can lower the organic electrocrystal, and the voltage is 0. Further, the cured film formed by the composition of the present invention can be coated not only by the inkjet method. The formation liquid can be applied by various methods such as spin coating or dipping, and is therefore an effective material in terms of productivity. [Embodiment] The present invention relates to an image forming underlayer comprising at least one compound selected from the group consisting of a polyimine precursor having a novel structure and a polyimine obtained from the polyimide precursor. Membrane composition. Further, the cured film (the underlayer film for image formation, the underlayer film for electrode pattern formation, the gate insulating film for an organic transistor) obtained by using the above composition, and an electronic device using the cured film. The details will be described below. [Polyimide precursor and polyimine obtained from the polyimide precursor] The present invention is an underlayer film composition for image formation which is selected from the following formulas (1) and (1a) And at least one compound of the group consisting of the polyimine precursor of the structural unit and the polyimine obtained by subjecting the polyimine precursor to dehydration ring closure to form a group of -12-201002762: [Chem. 6]

(1) (1a) (wherein A represents a tetravalent organic group 'B1 represents at least one divalent organic group represented by the above formula (2) 'B2 represents a divalent organic group, and R1, R2, Rla, and R2a each independently represent hydrogen The atom or the monovalent organic group, η is the total number of moles of the structural unit represented by the formula (1) 'm is the total number of moles of the structural unit represented by the formula (la), and η and m respectively represent a positive integer and satisfy 〇〇 1$n/(n + m)s〇.3) In the above formula (1) and formula (la), the structure of the organic group represented by A is not particularly limited as long as it is a tetravalent organic group. Further, in at least one compound selected from the group consisting of a polyimine precursor represented by the formula (1) and the formula (1 a) and a polyimine obtained from the polyimide precursor, A The structure of the organic group represented may be one type or a plurality of types. Specific examples of the organic group represented by A may be exemplified by the following organic groups of the formulae A-1 to A-36: -13- 201002762 [Chemical 7] (ΑΊ] tA*2] [Α·3] [A4] Know: 8: :mx :axc

[Α·6] [A-6] [A.7] [A-8I χΛχ xirSa χΛχ [A-9] [A-10] [A-11] [Chem. 8] XEvery item I! ^ [A- 12].【A-131 【A-14】 【A-15J 【A-16】 【A-17】

XX [Α·18][Α>19] [Α-20] [ Α-21 ] [ Α-22 ][Α·23 】 Take: πΤπ: :τφΤ〇: Disaster [Α-24] [Α-25 ] [Α·26] [Α·27]

XX: / [Α·33] [Α-34] [Ads] [Α-36] The above formulas Α-1 to Α-3 6 are appropriately selected depending on the characteristics required as the underlayer film for image formation. For example, in the above formulas Α1 to Α-36, Α-1 to Α-11 are polyfluorene precursors having a structural unit represented by the formulas (1) and (la) of -14 to 20,072,062 In the case of an imine, since the aromatic ring system is directly bonded to the quinone ring, it is considered that the insulating property is lowered (the leakage current is large), but it is directly bonded to the quinone ring in comparison with the aliphatic ring. It is characterized by a higher dielectric ratio. On the other hand, since Α-12 to Α-35 have an alicyclic structure in the base, it is not only highly insulating (leakage current is small), but also the amount of ultraviolet ray irradiation can be reduced by the change of the contact angle described later. The point of view is also better, especially Α-12 to Α-15 is the best. In addition, Α-17, Α-27, Α-29, Α-30, Α-31, Α-32 and Α-36 can change the contact angle and reduce the amount of ultraviolet radiation, and become polyimine It is also preferable because the solubility in the solvent is also high. Further, for the purpose of improving the solubility and reducing the amount of ultraviolet radiation necessary for the change in the hydrophilicity and hydrophobicity, a plurality of kinds of tetravalent organic groups having an alicyclic structure may be used in combination. In the above formula (1), Β1 is a divalent organic group having a fluoroalkyl group, and specifically, at least one divalent organic group represented by the following formula (2): [Chemical Formula 9] -〇τΧι, χ〆(7) , X! represents a single bond, -0-, -COO-, -oco-, -CONH-, -CH20- 'X2 represents a divalent organic group having 3 to 18 carbon atoms, and R3 represents a carbon number of 2 to 12 Perfluoroalkyl). -15- 201002762 The fluoroalkyl group represented by the above R3 has a low surface free energy and can impart high water repellency. However, if the number of carbon atoms is less than 2, high water repellency cannot be obtained, and if the number of carbon atoms is too long, not only the dialing number is not long. The reason why the water-based control becomes difficult and the specific dielectric ratio becomes low, the number of carbon atoms is preferably from 2 or more to 12, more preferably from 4 to 8. Further, although the fluorine content is increased, a higher water repellency can be obtained, but the long-chain alkyl group is completely fluorinated, and the ratio of the dielectric constant is greatly lowered. Therefore, by using a carbon chain such as an alkylene group which does not contain a fluorine atom as a spacer (X2 in the formula (2)), it is possible to suppress a decrease in specific dielectric constant and obtain high water repellency. X2 is a divalent organic group having 3 to 18 carbon atoms, more preferably 6 to 18 carbon atoms, and most preferably a valent organic group having 9 to 18 carbon atoms. X2 is not particularly limited as long as it is a divalent organic group having 3 to 18 carbon atoms, but is preferably selected from divalent hydrocarbon groups having an alkylene group, an aromatic ring or an aliphatic ring or both. In the formula (2), the above oxime 2 may be directly bonded to the benzene ring or may be bonded through a bonding group. That is, in the formula (2), Χι can be exemplified by a single bond, -〇-, -(:〇〇-, -OCO-, _c〇NH-, -CH2〇-. represented by the above formula (2) Specific examples of the divalent organic group are exemplified by the following formulas (12) to (15): -16 - 201002762 [化10] 〇^CH2)k(CF2), CF3 〇Y〇-(CH2)k (CF2 ), CF3 k«3~18,1=1-11 (12) 〇Y〇-Q-iCH2)k{CF2)ICF3 J〇T k*1~12fM~11 (14) k*3~18,N1 ~11 (13) °Y〇~(3^CH2)k(CF2)ICF3 k«1-12, Ι=1Ί1 (15) and 'represents the change in contact angle of hydrophilicity-hydrophobicity. It is caused by decomposition of the fluorine-containing side chain of B 1 in the formula (1) by ultraviolet irradiation. In addition, it is known that the tetravalent organic group represented by the above A is also decomposed by ultraviolet rays and the contact angle is largely changed (Patent Document 1). In the above formula (1), the divalent organic group having a fluoroalkyl group (the group represented by the formula (2)) represented by B1 can impart high water repellency even in a small amount. However, when the content is too large, the dielectric constant is lowered and the amount of hydrophilicity change due to ultraviolet irradiation is also small. Therefore, the divalent organic group represented by the following B2 is used. In the above formula (la), 'B2 is a divalent organic group' It is preferably an organic group which satisfies the following requirements. Conventionally, a long-chain side chain has been introduced for the purpose of imparting water repellency. However, the fluorine-based compound in the above-mentioned B1 group can impart high water repellency based on a small amount, so that the introduction ratio of long-chain side chains can be reduced. Therefore, from the viewpoint of imparting water repellency, that is, reducing the surface free energy, it is not necessary to use a long-chain base other than the fluorine-based base. Instead, it is less likely to be contained than the lower dielectric constant. -17-201002762 Further, the introduction ratio of the long-chain side chain is reduced, so that the density of the contact angle change portion (anhydride component) is increased, and it is preferable from the viewpoint that the sensitivity can be expected to be improved. In the present specification, the sensitivity refers to the degree of change from hydrophobicity to hydrophilicity per exposure amount (ultraviolet irradiation amount). In other words, the divalent organic group represented by B2 preferably has an aromatic ring from the viewpoint of satisfying the above conditions, and then efficiently absorbing ultraviolet rays and efficiently changing the contact angle. For example, an organic group represented by the following formulas (3) to (5) is preferred.

(wherein Y1 independently represents a single bond, an ether bond, an ester bond, a thioether bond, a guanamine bond, a pendant group having a branched structure of 1 to 3 carbon atoms or a carbon number of 1 to 3) The alkylenedioxy group γ2 having a branched structure represents a single bond, an ether bond, an ester bond, a thioether bond, or a guanamine bond, and r4 independently represents a hydrogen atom, a methyl group, an ethyl group, a trimethyl group, and R5 represents A hydrogen atom is a methyl group or a difluoromethyl group, and R6 represents a methyl group and an ethyl group. Each of j is a specific example of B2 represented by the above formulas (3) to (5), and is exemplified by the following B-1. To the B-23 two-valent organic base. -18- 201002762 [Chemical 12]

[Β-1] [Β-2] [Β-3] [Β-4] [Β-5] ΙΒ-6]

[Β-21] [Β-22] F3C cf3 xxQ^xb&lt;0xr In particular, Β-2, Β-3, Β-5, Β-10, Β-13 are highly soluble and can produce solubility with high solubility. Polyimine is therefore preferred. Further, the two-valent group represented by Β2 may be used in combination of two or more kinds from the viewpoints of solubility and reduction in exposure amount. Further, other 2 -19 to 201002762 valent organic groups having a long-chain alkyl side chain can also be used without lowering the specific dielectric constant. As described above, in the above formula (1), if the fluoroalkyl group contained in the B1 group is too large, the specific dielectric constant is lowered and the amount of change in the hydrophilicity due to ultraviolet irradiation is lowered, so that the above B2 is used. When the content of the fluoroalkyl group is too small, the water repellency of the unexposed portion is lowered, and the image forming liquid having a low surface tension cannot be patterned. Therefore, the ratio of the ratio of B1 to B2, that is, the ratio of η expressed in the formula (1) to m expressed in the formula (la) is preferably in the range of 〇.〇l$n/(n + m) &lt; Preferably, it is in the range of 〇.〇lSn/(n + m) &lt; 0.06. <<Method for Producing Polyimine Precursor>> The polyimine precursor containing the structural unit represented by the above formula (1) and formula (la) is obtained, and the tetracarboxylic acid represented by the following formula (16) can be obtained. The dianhydride component and the diamine component represented by the following formulas (17) and (18) are simply mixed in an organic solvent. Further, one type or two or more types of the tetracarboxylic dianhydride component and the diamine component may be used. [Chem. 14]

(16) H2N-Bi-NH2 (17) H2N-B2-NH2 (18) (wherein A is a tetravalent organic group, and B1 is a bivalent -20-201002762 machine group represented by the above formula (2), B2 is a divalent organic group other than B1). In the tetracarboxylic dianhydride component represented by the above formula (16), the specific example of the tetravalent organic group represented by A is exemplified by the above formula (A-1 to A.36), and the above formula (17) And, in the diamine component represented by (18), 'B1 is a divalent organic group which is a fluorine-containing compound base' is specifically represented by the above formulas (12) to (15). Further, specific examples of the divalent organic group represented by B2 include those represented by the above formulae B-1 to B-23. As described above, when A is preferably a tetravalent organic group containing a plurality of aliphatic rings, that is, the tetracarboxylic dianhydride component is preferably a ratio of aliphatic acid dianhydride. In this case, when a polyimide film is produced using an aromatic acid anhydride to form a cured film, when a high electric field is applied to the cured film, the insulating property is remarkably lowered. However, the aliphatic acid anhydride is excellent in insulation properties at a high electric field. For example, the operating voltage of the organic transistor is substantially about 1 MV/cm. In the case of this use, it is preferable to use an aliphatic acid anhydride as a raw material of the polyimide precursor from the viewpoint of insulating properties. As a method of mixing the tetracarboxylic dianhydride component and the diamine component in an organic solvent, a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and tetracarboxylic dianhydride is directly added or dispersed. a method of adding after dissolving in an organic solvent; instead, adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent; and adding a tetracarboxylic dianhydride component and a diamine component Method, etc. Further, the tetracarboxylic dianhydride component and the diamine component are a plurality of compounds, and the plurality of components may be polymerized in a state of being preliminarily mixed, and the polymerization may be carried out in sequence. The polyimine precursor used in the present invention is a compounding ratio of the two components when the tetracarboxylic dianhydride component represented by the above formula (16) and the diamine represented by the above formulas (17) and (18) are produced. That is, (the total number of moles of the tetracarboxylic dianhydride component): (the total number of moles of the diamine component) is preferably 1: 〇. 5 to 1: 1.5. As in the usual polycondensation reaction, the closer the molar ratio is to 1··1, the greater the degree of polymerization of the resulting polyimide precursor and the increase in molecular weight. In the method for producing the polyimine precursor, the temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent is usually from -20 to 15 (TC, preferably from 〇 to 80 °). C. If the reaction temperature is set to a relatively high temperature, the polymerization reaction is rapidly completed, but if it is too high, a high molecular weight polyimine precursor may not be obtained. Further, in a polymerization reaction in an organic solvent, in a solvent The solid content concentration of the two components (the tetracarboxylic dianhydride component and the diamine component) is not particularly limited, but if the temperature is too low, it is difficult to obtain a high molecular weight polyimine precursor, and if the temperature is too high, the reaction solution is too high. The viscosity becomes too high', and it becomes difficult to uniformly stir, so it is preferably from 1 to 50% by mass. More preferably from 5 to 30% by mass. The polymerization reaction is carried out at a high concentration in the initial stage of the polymerization (polyimine precursor) At the same time, it is also possible to add an organic solvent in the subsequent step. The organic solvent used in the above reaction is not particularly limited as long as it can dissolve the produced polyimide precursor, and the specific example can be exemplified by Ν, Ν -dimethyl methacrylate Indoleamine, N,N-dimethylacetamide, N-methyl-shame-22-201002762 ketone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, Dimethyl maple, hexamethyl sulfoxide 'γ-butyrolactone, etc. These may be used singly or in combination of two or more. Further, even if the solvent of the polyimide precursor is not dissolved, as long as it is not The precipitated polyimine precursor may be mixed in the solvent. The solution containing the polyimine precursor obtained above may be directly used in the preparation of the image forming the underlying film. In addition, the polyimide precursor can also be precipitated and isolated in a weak solvent such as water, methanol or ethanol, and used after recycling. "Conversion to polyimine" has the formula (1) and The polyimine precursor of the structural unit represented by (la) may be a polyfluorene ring by dehydration ring closure. The method of the ruthenium imidization reaction is not particularly limited, but a catalyst of an alkaline catalyst and an acid anhydride is used. Imidization in the ruthenium imidization reaction tends to cause the molecular weight of polyimine and the sulfhydrylation rate is easy to control. The ruthenium imidization can be carried out by stirring the above-mentioned polyfluorinated precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 1 hour. The imidization precursor may also be used as a solvent containing a polyimine precursor obtained by polymerizing the above tetracarboxylic dianhydride component and a diamine component directly (not separately). For example, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., among which pyridine has a base which is suitable for the reaction, is preferably -23-201002762. The acid anhydride may be exemplified by acetic anhydride and benzoic acid. An acid anhydride, pyromellitic anhydride, etc. Among them, acetic anhydride can be preferably purified by purifying the polyimine after the imidization of the hydrazine. As the organic solvent, the polymerization reaction of the polyimine precursor can be used. Solvent. The reaction temperature at which the catalyst is imidized is preferably from -20 to 250 ° C, more preferably from 0 to 180 ° C. When the reaction temperature is set to a high temperature, the imidization speed is increased, but if it is too high, the molecular weight of the polyimine is lowered. The amount of the basic catalyst is preferably from 0.5 to 30 moles, more preferably from 2 to 20 moles, relative to the acid amide group in the aforementioned polyimide intermediate. Further, the amount of the acid anhydride is preferably from 1 to 50 moles, more preferably from 3 to 30 moles, relative to the acid amide group in the polyimide precursor. The ruthenium imidization ratio of the obtained polyimine can be controlled by adjusting the above reaction temperature and the amount of the catalyst. The reaction solution of the solvent-soluble polyimine obtained as described above can be directly used for the production of the gate insulating film described later. However, since the reaction solution contains a ruthenium-based catalyst, the polyimine is preferably purified. It is recycled and washed and used in the production of membranes. The polyimine is recovered by a simple method in which the reaction solution is added to a weak solvent in a stirred state to precipitate a polyimine and filter it. The weak solvent to be used at this time is not particularly limited, but may be exemplified by methanol, hexanol, gadolinium, ethanol, toluene, water, and the like. After filtering and recovering a few halls, it is better to wash with the above weak solvent. -24- 201002762 The recovered polyimine can be dried at room temperature or under reduced pressure to form a polyimide pigment at normal temperature or under heat. Further, the polyimine powder can be further dissolved in a good solvent, and re-precipitation in a weak solvent is repeated 2 to 10 times to make the impurities in the polymer less. The good solvent to be used at this time may, for example, be hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, 2-pyrrolidone, hydrazine-methyl-2-pyrrolidone, hydrazine - Ethyl-2-pyrrolidone, fluorene-vinyl-2-pyrrolidone, hydrazine-methyl caprolactam, dimethyl arylene, tetramethylurea, γ-butyrolactone, and the like. These may be used singly or in combination. Further, when a weak solvent used for reprecipitation is used, three or more kinds of weak solvents such as alcohols, ketones, and hydrocarbons can be used to further improve the purification effect. [The underlayer film composition for image formation] The underlayer film composition for image formation of the present invention contains the polyimine precursor and/or the polyimine and a solvent, and may further contain a crosslink which will be described later as needed. A composition of a agent or a surfactant or the like. The molecular weight of the polyimine precursor and/or polyimine used in the composition for forming an underlayer film for image formation of the present invention is a viewpoint of stability in terms of ease of handling and solvent resistance at the time of film formation. It is desirable to use a weight average molecular weight (result as measured by GPC) of preferably from 2,000 to 200,000, more preferably from 5,000 to 50,000. When the cured film is formed by using the underlayer film composition for image formation of the present invention, and when it is irradiated with ultraviolet rays, there is no difference between the amine precursor and the polyimine which is related to the amount of change in the hydrophilicity. Large differences, so when the resulting cured film can provide the focus of this aspect, the yield of hydrazine is not particularly limited. However, by using polyimine, the polarity of the polyimide can be compared with that of the plastic substrate, which can be obtained at a lower temperature (less than 180 ° C). Since the polyimine precursor is extremely low, the advantage of increasing the contact angle of water before the irradiation of the external line (high hydrophobicity) can be obtained, so that the polyimide is more preferably used. In the underlayer film composition for image formation of the present invention, it is assumed that the electrode for an organic transistor used as a main application is required not only as a function as an underlayer film for image formation but also as a high insulating property. When a cured film (for example, a drain insulating film) is used as the main point of the insulating property, it is preferred that the polyimide which is imidized by the polyimide precursor is directly dissolved in a solvent to form an underlayer for image formation. Membrane composition. In this case, when the polysiane ratio is high, the solvent solubility is lowered. However, the niobium imidization ratio is preferably as high as possible within a range not impairing the solubility, specifically, 80% or more, more preferably 90% or more. In the present invention, the term "imidization ratio" refers to the dissolution of polyimine in d6-DMSO (dimethyl azo-d6). 1H-NMR measurement, the number of protons and aromatic protons The ratio of the number 'calculates the ratio of proline acid remaining in the imidization to calculate the sulfhydrylation rate. The solvent used in the composition of the underlayer film for image formation of the present invention is not particularly limited as long as it can dissolve the polyimide precursor or the polyimine, and is exemplified by N,N-dimethylformamide. Ν,Ν·Dimethylacetamide, 2-pyrrolidone, Ν·methyl-2-pyrrolidone, Ν-ethyl·2-pyrrolidone, Ν _vinyl- -26- 201002762 2- A good solvent such as pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, γ-butyrolactone or the like. These may be used singly or in combination, and may be used by mixing a weak solvent such as an alcohol, a ketone or a hydrocarbon in the above-mentioned good solvent. In the underlayer film composition for image formation of the present invention, the total mass ratio of the polyimide precursor and/or the polyimide may be uniformly dissolved in the solvent as long as the polyimide precursor and/or the polyimide may be uniformly dissolved in the solvent. There is no particular limitation, and for example, it may be 1 to 30% by mass, and for example, 5 to 20% by mass. The method for preparing the underlayer film composition for image formation of the present invention is not particularly limited, and a solution containing a polyimine precursor obtained by polymerizing the above tetracarboxylic dianhydride component and a diamine component may be used as it is or The reaction solution of the polyimine obtained by using the solvent can be used as it is. Further, in the composition for forming an underlayer film for image forming of the present invention, in order to improve the adhesion between the composition and the substrate, a crosslinking agent may be further contained as long as the effects of the present invention are not impaired. The above-mentioned crosslinking agent may, for example, be a compound containing a functional decane or a compound containing an epoxy group, and specific examples thereof include 3-aminopropyltrimethoxydecane and 3-aminopropyltriethoxy Baseline, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, hydrazine- (2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxy Carbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-trimethoxydecylpropyltriazine, N-triethyl Oxidylalkylpropyltriethylethylamine-27- 201002762, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethane-1,4,7-three Azadecane, 9-trimethoxydecyl-3,6-diazoacetate, 9-triethoxydecyl-3,6-diazaindolyl-3-amine Propyltrimethoxydecane, N-benzyl-3-aminopropyl decane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene; Propyl triethoxy decane, N-bis(oxyethyl)-3-aminopropyl decane, N-bis(oxyethyl)-3-aminopropyltriethoxystanol Diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol glyceryl ether, tripropylene glycol diglycidyl ether, polypropylene glycol dihydrate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl oil Diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyltoluenediamine, 1 , 3-bis(indole, fluorene-diglycidylaminomethyl)cycloindole ratio ^[',1^'-tetraglycidyl-4,4'-diaminodiphenylmethane or the like. These may be used alone or in combination of two or more. When the coupling agent is used, the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 20 parts by mass, per 100 parts by mass of the substrate for image formation. Further, in the underlayer film composition for image formation of the present invention, the coating property of the composition and the film thickness of the film obtained from the composition are both surface smoothness, and may also contain a surfactant. The surfactant is not particularly limited, and examples thereof include a surfactant, a lanthanoid surfactant, a nonionic interfacially active oxonium group, Ν-benzyltriethoxy-3-amine-trimethoxy, The bis-glycidyl ether ether, the glycerol, the 6-tetra-m-dihexane, and the chemical layer film group are preferably 1 for the purpose of improving oneness or a fluorine-based agent. -28 - 201002762 As such a surfactant, for example, F TOP EF301, EF303, EF3 52 (manufactured by JEMUYU Co., Ltd.), MEGAFAX F 1 7 1 'F 1 7 3, R-3 0 (Daily Ink Chemistry) Industrial (share) system, FLORIDE FC430, FC43 1 (Sumitomo 3M (share) system), ASAHIGUAID AG7 1 0, SURFLON S-3 82, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (share)), etc. . When the surfactant is used, the content thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the underlayer film composition for image formation. [Polymer Blend] The underlayer film composition for image formation of the present invention may be mixed with other polymers capable of forming a film (for example, high in addition to the polyimine precursor of the present invention and/or polyimine. Insulating polymer), the so-called polymer blend morphology. In the polymer blend, by adjusting the structure of the polymer (the polyimine precursor of the present invention, polyimine, and other polymers), the film can be formed in the film at the time of formation of the cured film. The concentration gradient of each polymer is generated in the thickness direction, so that it can be utilized as a useful means. For example, since the change in hydrophilicity is a problem only for the surface of the film, the fluoroalkyl group-containing polyimide precursor and/or polyimine of the present invention is present only in the upper layer of the cured film. The surface layer can be. Therefore, when the above-mentioned image forming underlayer film composition is used as a polymer blend form, 'as a polyimine precursor of the present invention or a polyimine bond -29-201002762, the ratio is relative to the blending polymerization. The total mass of the substance is from 1% by mass to 1% by mass. When it is 1% by mass or less, the polyimine precursor or the polyimine of the present invention having the outermost surface of the film formed is too small, and the image forming ability is deteriorated. The above-mentioned polymer-derived compound can be exemplified by the use of the underlayer film composition for image formation of the present invention in the use of a gate insulating film which is particularly required to have high insulating properties. When it is used for a gate insulating film, the coating liquid is required to have a firing temperature corresponding to 180 ° C or lower, a film formation by coating, and a solvent resistance to an organic semiconductor coating liquid (xylene, There are several characteristics such as a non-polar solvent such as trimethylbenzene and a low water absorption rate, but it is required to have the highest performance in terms of insulation. In order to achieve such high insulation properties, the composition of the underlayer film for image formation of the present invention has a ruthenium amination rate of at least 8 〇% or more, and depending on the case, it is required to be 90% or more. When the rate exceeds 90%, the solubility of the solvent is also lowered. In this case, the high insulating layer is located only in the lowermost layer of the insulating film, and the layer composed of the underlayer film composition for image formation of the present invention is located in the upper layer, thereby maintaining the high insulating property and solubility problem of the insulating film. Can also be dissolved. The above can be obtained by sequentially laminating the lower layer of the cured film as a high insulating layer and the upper layer as a hydrophilic-hydrophobic conversion layer, but the operation is cumbersome. At this time, the material of the high insulating layer is mixed with the material of the hydrophilic-hydrophobic conversion layer (that is, the polyimide precursor of the present invention and/or the polyimine), and at this time, if the polarity or molecular weight of the upper material is set If it is smaller than the lower layer, then -30-201002762, the mixture is coated on the substrate and dried, and during the evaporation of the solvent, the upper layer material shows the movement to the surface forming layer, so the above concentration gradient can be easily controlled (this The so-called layer separation). The material for forming the high insulating film which can form the lower layer described above is preferably a soluble polyimine. When a soluble polyimine is used as the underlayer material, the sulfonium imidization ratio of the polyimine in the solution is preferably at least 50% or more, preferably 80% or more, from the viewpoint of insulation. It is preferably 90% or more. As the other material which can be used as the underlayer material, a general organic polymer such as an epoxy resin, an acrylic resin, a polypropylene, a polyvinyl alcohol, a polyvinyl phenol, a polyisobutylene, a polymethyl methacrylate or the like can be exemplified. Further, the above polymer blend is used, for example, in the case of an organic crystal crystal having a film thickness of about 40 Onm, and the polyimine precursor and/or polyazide of the present invention which is provided in the upper layer (hydrophobic interaction layer) The content ratio of the amine to the polymer blend is theoretically about 1%, but if it is too small, the in-plane deviation of the surface property of the cured film becomes large, so the polyimine precursor and/or the poly The quinone imine preferably contains at least 5% or more. [Manufacturing Method of Coating Film and Cured Film] The underlayer film composition for image formation of the present invention can be subjected to a dipping method, a spin coating method, a transfer printing method, a roll coating method, an inkjet method, a spray method, or a brush. Coating, etc., coated on a general-purpose plastic substrate or glass substrate of polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, polyether oxime, polyethylene naphthalate, polyimine, etc. On the other hand, subsequently, pre-drying is performed by a hot plate or an oven - 31 - 201002762, etc., thereby forming a coating film. Subsequently, it can be used as an underlayer film or a cured film for image formation by the heat treatment. The above heat treatment method is not particularly limited, but a method of performing a hot plate or an oven in an appropriate atmosphere, that is, air, nitrogen, or the like, or a vacuum may be exemplified. The firing temperature is determined by the thermal enthalpy sub-point of the polyimide precursor, preferably from 180 ° C to 250 ° C, and is preferably formed on a plastic substrate, preferably 1 80 °. Below C. The firing can also be carried out with a temperature change of two or more stages. The order can further improve the uniformity of the obtained film. Further, when the cured film is produced, since the underlayer film for image formation contains a polyimide precursor and/or a polyimide and the above solvent, it can be directly used for coating the substrate, but the flatness of the film is adjusted. The purpose of improving the wettability of the coating liquid on the substrate, adjusting the surface tension, the polarity, the boiling point, and the like may be carried out by adding a solvent other than the above solvent. Specific examples of such a solvent include, in addition to the second stage agent of the above second page, ethyl cellosolve, butyl cellosolve 'alcohol, butyl carbitol, ethyl carbitol acetate, Ethylene glycol and the like 2-propanol, 1-ethoxy-2.propanol, 1-butoxy-2-propanol-2-propanol, propylene glycol monoacetate, propylene glycol diacetate 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-ethylenepropanediol, 2-(2-methoxypropoxy)propanol, 2-(2-ethoxyl) The coating film is subjected to an insulating film by using an inert gas aminating film. The segmental firing composition is in the form of 'or ensuring that the coating liquid can be further added to the dissolved ethyl card; 1 -Methoxy:, 1-phenoxy, propylene glycol-ester, dipropoxy) propyl-32-201002762 Alcohol and propylene glycol derivatives such as 2-(2-butoxypropoxy)propanol, methyl lactate A lactate derivative such as ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate. These can be used alone or in combination. Moreover, from the viewpoint of improving the preservability of the composition for forming an underlayer film for image formation and the film thickness uniformity of the coating film, 20 to 80% by mass of the total amount of the solvent is preferably selected from N,N-dimethyl group. At least one solvent of decylamine, N,N-dimethylacetamide, N-methyl-2-la-squalanone, γ-butyrolactone, dimethyl argon. The concentration of the underlayer film composition for image formation is not particularly limited, but is preferably from 0.1 to 30% by mass, more preferably from 1 to 10% by mass of the solid content of the polyimide and the polyimide. 10% by mass. It can be arbitrarily set depending on the type of the coating device or the film thickness to be obtained. When the cured film of the present invention produced as described above is used as an underlayer film for image formation, if the film thickness is too small, the patterning property after ultraviolet irradiation is lowered, and if it is too thick, the surface uniformity is impaired. Therefore, as the film thickness thereof, it is preferably from 5 nm to 100 nm, more preferably from 10 nm to 300 nm, most preferably from 20 nm to 10 nm, and the cured film of the present invention can also function as an insulation when the insulating property is sufficiently high. Membrane function. At this time, the cured film is used as a gate insulating film which is disposed on the direct gate electrode in, for example, an organic FET device. In this case, the film thickness of the cured film is required to ensure insulation, and it is preferable to have a thickness thicker than that used when the underlayer film for image formation is used. The thickness thereof is preferably from 2 Å to 100 nm, more preferably from 50 nm to 800 nm, and most preferably from 10 Å to 500 nm to 33 to 201002762. [Use as an underlayer film for image formation: Method for producing an electrode for image formation The underlayer film for image formation of the present invention is irradiated with ultraviolet rays in a pattern shape, and then an image forming liquid described later is applied to produce an electrode for image formation. In the present invention, the method of irradiating ultraviolet rays in a pattern shape in the image forming underlayer film of the present invention is not particularly limited, and for example, a method of irradiating a mask with a pattern of an electrode pattern can be used, and a laser light pattern is used. The method of the electrode pattern and the like. The material and shape of the mask are not particularly limited as long as the region necessary for the electrode is ultraviolet-transmitting, and the region other than the ultraviolet-ray transparent property may be used. In this case, it is generally possible to use an ultraviolet ray having a wavelength in the range of 200 nm to 500 nm, and it is preferred to select an appropriate wavelength depending on the type of polyimine used to pass through a filter or the like. Specifically, wavelengths of 248 nm, 2 54 nm, 303 nm, 313 nm, 3 65 nm, and the like are exemplified. It is preferably 248 nm or 2 5 4 nm. The underlayer film for image formation of the present invention gradually rises in surface energy by irradiation of ultraviolet rays, and saturates with a sufficient amount of irradiation. This increase in surface energy causes a decrease in the contact angle of the image forming liquid, and as a result, the wettability of the image forming liquid in the ultraviolet ray irradiation portion is improved. Therefore, when the image forming liquid is applied onto the underlayer film for image formation of the present invention after ultraviolet irradiation, the image is formed along the pattern shape of the underlayer film for image formation by the surface energy difference. The forming liquid will self-organize to form a pattern, and an electrode of any pattern shape can be obtained. -34-201002762 For this reason, it is necessary to irradiate the amount of ultraviolet irradiation to the image forming underlayer film to sufficiently change the contact angle of the image forming liquid, but the energy efficiency and the time of the manufacturing process are shortened. It is preferably 40 J/cm 2 or less, more preferably 20 J/cm 2 or less, and most preferably i 〇 j / cm 2 or less. Further, the larger the contact angle difference between the ultraviolet ray irradiation portion of the underlayer film for image formation and the image forming liquid of the non-irradiation portion, the easier the patterning becomes, and the processing of the electrode of a complicated pattern or a fine pattern shape becomes may. When a solution having a low surface tension is used, the difference in contact angle between the exposed portion and the unexposed portion is 5. Preferably, the above is better than 1 〇 ° or more, and the optimum is more than 20 °. Therefore, it is only necessary to appropriately optimize the application method of the image forming liquid, the surface tension of the image forming liquid, the image refinement, and the film flatness. For the same reason, the contact angle of the image forming liquid is preferably 30 or more in the ultraviolet non-irradiated portion, and the ultraviolet irradiation portion is preferably 20 or less. The image forming liquid in the present invention is a coating liquid which can be used as a functional film after being applied onto a substrate and evaporating the solvent contained therein, for example, dissolved or uniformly dispersed in at least one solvent. Charge transporting substance. Here, the charge transport property means that it is synonymous with conductivity, and is any one of charge transportability, electron transport property, and charge transportability of electrons and electrons. The charge transporting material is not particularly limited as long as it has conductivity capable of transporting holes or electrons. Examples thereof include metal fine particles such as gold, silver, copper, and aluminum, or inorganic materials such as carbon black, fullerene, and carbon nanotubes, or polythiophene, polyaniline, polypyrrole, and poly. An organic π-conjugated polymer or the like of such derivatives. -35- 201002762 In addition, in order to improve the charge transport energy of the charge transporting material, halogen, Lewis acid, protic acid, and transition metal compounds may be further added to the image forming liquid (specific examples are Br2, I2, FeCl3, Charge accepting substances such as MoC16, BF4, AsF6, S04, HN〇4, H2S〇4, polystyrenesulfonic acid, etc., or alkali metal or alkylammonium ions (specific examples are Li, Na, K, C s A charge-donating substance such as tetraethylammonium or tetrabutylammonium or the like is used as a dopant. The solvent of the image forming liquid is not particularly limited as long as it can dissolve or uniformly disperse the above-mentioned charge transporting substance or dopant. The surface tension of the image forming liquid is preferably from 25 mN/m to 50 mN/m from the viewpoint of obtaining the electrode image (pattern) correctly. When the surface tension is excessively lower than the above range, the ultraviolet irradiation portion cannot exhibit a sufficiently large contact angle, and if the surface tension is excessively higher than the above range, the contact angle of the ultraviolet irradiation portion becomes high, and the irradiation amount of the ultraviolet ray is increased, which is not preferable. The solvent for the image forming liquid is not particularly limited, and various organic solvents such as alcohols, ketones, ethers, esters, aromatic hydrocarbons, and glycols can be used. Examples of the alcohols include methanol, isopropanol, n-butanol, isobutanol, second butanol, isoamyl alcohol, and octanol. Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone diacetone alcohol, and the like. Examples of the ethers include ether, isopropyl ether, dioxane, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Examples of the vinegar include ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, cellosolve acetate, fatty acid methyl ester, and the like. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and trimethylbenzene. -36-201002762 Examples of the aliphatic hydrocarbons include n-hexane, isohexane, cyclohexane, mineral waste, n-pentane, and the like. Examples of the glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether. Further, from the viewpoint of excellent solubility of the organic charge transporting substance, N,N-dimethylformamide, n,N-dimethylacetamide, 2-pyridinone are also preferable. , N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, four A polar solvent such as methyl urea, but these are preferably used in a range in which damage to the underlayer film for image formation of the present invention is small. Further, although a solvent having a particularly large surface tension such as water can be used, it is preferred to adjust the surface tension by adding a surfactant or the like. The concentration of the charge transporting substance in the image forming liquid is preferably from 0.01 to 30% by mass, more preferably from 0.1 to 10% by mass, most preferably from 1 to 5% by mass, based on the image forming liquid of the present invention. Specific examples include a conductive polymer solution such as Baytron (registered trademark) P (polyethylenedioxythiophene, manufactured by Bayer), DOTITE XA-9069 (manufactured by Fujikura Kasei Co., Ltd.), and W4A (manufactured by Sumitomo Electric Co., Ltd.). A silver fine particle dispersion liquid such as NPS-J (manufactured by HARIMA Chemical Co., Ltd.). The electrode of the present invention is produced by applying the image forming liquid onto the underlayer film for image formation of the present invention, forming an image, and evaporating the solvent. The solvent evaporation method is not particularly limited, but it can be evaporated by using a hot plate or an oven under an appropriate atmosphere, that is, an inert gas such as air or nitrogen, or a vacuum to obtain a uniform film formation surface. -37- 201002762 The solvent evaporation temperature is not particularly limited, but is preferably carried out at 40 to 250 °C. In order to maintain the shape of the underlayer film for image formation and to achieve uniformity after film formation, temperature changes of two or more stages may be employed. The electrode formed by the image forming liquid can be used not only as a wiring for connecting electronic devices but also as an electrode of an electric device such as an electric field effect transistor, a bipolar transistor, various diodes, various sensors, or the like. . The electronic device of the present invention may be an electrode made of an image forming liquid formed on the underlayer film for image formation of the present invention. Hereinafter, an example in which the underlayer film for image formation of the present invention is used for an organic FET device is shown, but the present invention is not limited thereto. First, a glass substrate having an I TO electrode is formed on one surface. Preferably, the substrate is washed with a liquid such as a lotion, alcohol or pure water in advance, and subjected to surface treatment such as ozone treatment or oxygen-plasma treatment just before use. On the substrate with the ITO electrode, a polyimine precursor having a structural unit represented by the above formula (1) and formula (la) is formed in the order of [the method for producing a coating film and a cured film] / or layer of polyimine. The film thickness of the layer is preferably from 100 nm to 100 nm in terms of both the driving voltage and the electrical insulating property. Subsequently, ultraviolet rays are irradiated in a pattern shape using a photomask or the like. Next, an image forming liquid using a low surface tension solvent such as PGME is applied onto the surface of the underlayer film for image formation. The applied image forming liquid is rapidly expanded in the hydrophobic portion (ultraviolet-irradiated portion) by the hydrophilic portion (ultraviolet-irradiated portion) to be stabilized, and dried to form a patterned source and gate electrode. The coating method of the image forming liquid is not particularly limited to the spin coating method or the casting method, but it is preferably an ink jet method or a spray coating method which is easy to control the amount of liquid -38-201002762 Finally, by pentazenes ( An organic semiconductor material such as Pentacene) or polythiophene is formed into a film to complete an active layer of an organic FET. The film forming method of the organic semiconductor material is not particularly limited, and examples thereof include, for example, a vacuum vapor deposition or a solution spin coating method, a casting method, an inkjet printing method, or a spray coating method. As described above, the organic FET produced can greatly reduce the number of fabrication steps, and further, since an organic FET having a shorter channel than the mask vapor deposition method can be fabricated, even when a low mobility organic semiconductor material is used as the active layer, Get a large current. Further, as the insulating film for the organic transistor, a film having a dielectric constant of 3.0 or more may be used. The underlayer film for image formation obtained by the method of the present invention has excellent electrical insulating properties and also has a dielectric constant as high as 3 _0, so that it can also be used as a gate insulating layer (insulating film), and the manufacturing steps can be simplified. Chemical. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an embodiment of the present invention, but the present invention is not limited to the above. [Measurement of 2P average molecular weight and weight average molecular weight of stomach] The number average molecular weight (hereinafter referred to as Μη) and the weight average molecular weight (hereinafter referred to as Mw) of the polyimide intermediate precursor obtained by the following synthesis method are by GPC (normal temperature) The gel permeation chromatography method was measured in the following apparatus and measurement conditions at -39-201002762, and was calculated as polyethylene glycol (or polyethylene oxide). GPC device: Shodex (registered trademark) (GPC-101) manufactured by Showa Denko Electric Co., Ltd. Pipe column: Shodex (registered trademark) manufactured by Showa Electric Co., Ltd. (KD803, K D 8 0 5 series)

Column temperature: 50 ° C Dissolution: hydrazine, hydrazine-dimethylformamide (as an additive for lithium bromide monohydrate (LiBr. Η2〇) 3 〇 millimoles / liter, phosphoric acid · anhydrous crystals (〇-phosphoric acid 30 mmol/L, tetrahydrofuran (THF) 10 ml/L) Flow rate: 1. 〇ml/min calibration line for standard preparation: TSK standard polyethylene oxide manufactured by Tosoh Co., Ltd. (molecular weight: 900,000, 150,000, 100,000, 30,000) Polyethylene glycol manufactured by POLYMER ROBOLABO Co., Ltd. (molecular weight: about 1 2,000 '4,000, 1,000) [Measurement of film thickness] The film thickness of polyimine is a part of the peeling film of the cutter, and it is fully automatic. The micro shape measuring machine (ET4000A, manufactured by Kosaku Seisakusho Co., Ltd.) was measured by measuring the measurement force at 1 〇 μΝ and the scanning speed at 0.05 mm/sec. [Ultraviolet irradiation] The ultraviolet ray was irradiated onto the polyimide film by a filter with a light source of a high-pressure mercury lamp as a light source at a wavelength of 254 nm -40 - 201002762. Further, the ultraviolet illuminance on the polyimide film was multiplied by the exposure time as the exposure amount (J/cm 2 ) on the polyimide film. The illuminance of the above-mentioned ultraviolet ray was measured by a probe for Deep UV having a sensitivity of 253.7 nm and mounted on an illuminometer (Model 3 〇 6 by AI), and the obtained illuminance was 45 to 50 mW/cm 2 . [Measurement of contact angle] The contact angle is measured in a constant temperature and humidity environment (25 °C ± 2 °C, 50% RII ± 5%) using a fully automatic contact angle meter CA-W (Concord Interface Science ( ()))). Further, the contact angle of propylene glycol monomethyl ether (PGME) was measured by a liquid amount of 3. 〇 to 3.5 μl after standing for 5 seconds, and the contact angle of pure water was 3 μl at the standstill after standing. It was measured in 5 seconds. &lt;Synthesis Example 1&gt; Polymerization of polyimine precursor (PI-1) was carried out in a nitrogen stream, and in a 50 ml 4-necked flask, 1.8823 g (0.0094 mol) of 4,4'-diamino group was charged. Diphenyl ether (hereinafter referred to as 〇DA) and 0.3579 g (0.0006 mol) of 3,5-diaminobenzoic acid η-(perfluoro-n-hexyl)-n-undecyl ester (hereinafter referred to as 八? :11-6?), after dissolving in 23.58 g of heart methyl-2-pyrrolidone (hereinafter referred to as NMP), adding 1.921 g (0.0098 mol) of 1,2,3,4-cyclobutane tetracarboxylate Acid dianhydride (hereinafter referred to as 080 persons), which was stirred at 23 ° C for 12 hours for polymerization, and further diluted with NMP to obtain -6 - 201002762 to obtain the mass of the polyimine precursor (P I-1) % solution. The number average molecular weight (?n) and weight average molecular weight (Mw) of the obtained polyimine precursor (P1-1) were Mn = 35,200, Mw = 83,60 Å, respectively. &lt;Synthesis Example 2&gt; The ruthenium imine (PI-2) was polymerized in a nitrogen stream and charged with 〇dA 3.3 5 0 1 g (0.0 1 67325 mol) and 1.6164 g (0.004462 mol) in a 1 ml ml 4-neck flask. 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane (post AMF), APC11-6F 0.6965 g (0.0011155 mol), after dissolving in 49.44 g NMP, add 6.698 1 g (0.022 3 1 mol) of 3,4-dicarboxy-1,2,3,4-tetra Hydrogen-1-naphthalene succinic dianhydride (hereinafter referred to as butyl octa), which was stirred at 50 ° for 24 hours to carry out polymerization, and the obtained polyaminic acid solution was diluted to 8 mass% with NMP. Adding 22.1 g of acetic anhydride and 1 〇.3 g of pyridine as a ruthenium amide catalyst to react at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol to filter the white precipitate obtained. 'When dried, a white polyimine powder was obtained. The polyiminoimine powder was confirmed to be imidized by more than 90% by iH-NMR. 4 g of this powder was dissolved in 30 g of γ-butyrolactone and In a mixed solvent of 6 g of dipropylene glycol monomethyl ether, a solution of 1 〇 mass% of polyimine (ΡI - 2) was obtained. The number average molecular weight (Μη) and weight average molecular weight of the obtained polyimine (ΡΙ-2) (Mw) is Mn = 13,900, Mw = 28,400, respectively. -42 - 201002762 &lt;Synthesis Example 3&gt; Polymerization of polyimine (PI-3) in a nitrogen stream at 50 ml In a 4-necked flask, 2.7769 g (0.0095 mol) of 1,3-bis(4-aminophenoxy)benzene (hereinafter referred to as DA-4P) and APC11-6F 0.3122 g (0.0005 mol) were charged. After dissolving in 21.96 g of NMP, add 2 to 402 g (0.0099 mol) of bicyclo[3.3.0]-octane-2,4,6,8-tetracarboxy dianhydride (hereinafter referred to as 8-8), The polymerization reaction was carried out at 40 ° (: stirring for 24 hours, and the obtained polyaminic acid solution was diluted to 8 mass% with NMP. To 23 g of this solution, 8.5 g of acetic anhydride and 3 - 9 g of pyridine were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 1 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white powder was filtered and dried to obtain a white polyimine powder. This polyimine powder was confirmed to be imidized by 90% or more by 1 H-NMR. 3 g of this powder was dissolved in a mixed solvent of 22.5 g of γ-butyrolactone and 4.5 g of dipropylene glycol monomethyl ether to obtain a 10% by mass solution of polyimine (ΡΙ-3). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (?-3) were Mn = 19,300 and Mw = 50,300, respectively. &lt;Synthesis Example 4&gt; Polymerization of polyimine precursor (PI-4) in a nitrogen gas stream was carried out in a 100 ml 4-necked flask, 〇d A 2.8234 g (0.0141 mol) and APC11-6F 0.5620 g. (0.0009 mol), after dissolving in 36_97 g of NMP, add 3.1084 g (〇.01425 mol-43-201002762) pyromellitic dianhydride (hereinafter referred to as PMDA), and stir it at 23 ° C for 5 hours. The polymerization reaction was further diluted with NMP to obtain an 8 mass% solution of a polyimine precursor (PI-4). The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine precursor (P 1-4) were Mn = 15,500 and Mw = 35, respectively. &lt;Comparative Synthesis Example 1 &gt; Polyimine imine precursor (PI-5) was polymerized in a nitrogen stream, and a 1-ml alkane oxide of 1.0565 (0.040 mol) was charged in a 200 ml 4-necked flask. Base-2,4-diaminobenzene (hereinafter referred to as APC18), after dissolving in 1 27.6 g of NMP, adding 7.45 g (0.03 8 mol) of CBDA, and stirring at 12 ° C for 12 hours to carry out polymerization. The solution was diluted with NMP to obtain a 2% by mass solution of polyglycine (PI-5). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyamic acid (PI-5) were Mn = 1 6,000 and Mw = 48,000, respectively. &lt;Comparative Synthesis Example 2 &gt; Polymerization of polyimine precursor (ΡΙ·6) was carried out in a nitrogen stream with a ODA of 2.9856 g (0.01491 mol) and APC11-6F 0.0562 g in a 50 ml 4-necked flask. (0.00009 mol), after dissolving in 24.93 g of hydrazine, adding 2.7946 g (0.01425 mol) of CBDA, stirring it at 23 ° C for 12 hours, and then diluting with NMP to obtain a polybendimimine precursor (PI) -6) 6 mass% solution. The number average molecular weight (??) and the weight average molecular weight (Mw) of the obtained polyimine precursor (p1-6) were Mn = 14, 2, and Mw = 28,500, respectively. A list of tetracarboxylic dianhydrides and diamines used in the synthesis examples and comparative synthesis examples is shown below. [Table 1] (Table 1) Synthesis Example and Comparative Synthesis Example used in dicarboxylic acid di-hepatic acid and diamine tetracarboxylic acid 1 dianhydride------two/, --&quot; two----- Amine-CBDA TDA BODA PMDA ODA DA-4P AMF APC11-6F _APC18_ PI-1 100 94 6 PI-2 100 75 20 5 PI-3 100 95 5 PI-4 100 94 6 PI-5 100 100 PI-6 100 99.4 0.6 *1: The numbers in the table indicate the molar fraction of the nominal tetracarboxylic dianhydride in the tetracarboxylic dianhydride, or the molar fraction of each diamine in all diamines. &lt;Example 1: Ultraviolet sensitivity characteristic (contact angle of PGME) of a polyimide film formed of PI-1&gt; On a glass substrate (2.5 cm square, thickness 〇.7 mm) with ITO attached A solution of PI-1 prepared in Synthesis Example 1 was dropped by a syringe equipped with a 0.2 μm pore filter, and coated by a spin coating method. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a heated plate for 30 minutes to obtain a polyimide film having a film thickness of about 40 nm. The PGME contact angle of this polyimide film was measured. The polyimide film obtained in the same order was irradiated with -45-201002762 ultraviolet rays of an irradiation amount of 6 J/cm 2 to measure the contact angle of PGME. &lt;Example 2 to Example 4, Comparative Example 1, and Comparative Example 2: Ultraviolet sensitivity characteristics (contact angle of Pgme) of a polyimide film formed of p丨_ 2 to PI_6 &gt; Synthesis Example 2 was used. In the synthesis example 4, the comparative synthesis example 1 and the comparative synthesis example 2, the p I - 2 to PI - 6 solution was prepared, and the polyimide film was produced in the same procedure as in the example 1 'measured without irradiating ultraviolet rays, and irradiating 6 j / Cm 2 PGME contact angle after UV. The measurement results of the PGME contact angle are shown in Table 2. [Table 2] (Table 2) PGME contact angle number before and after ultraviolet irradiation using PI composition not irradiated 6J/cm2 Contact angle difference PI acid diamine*1 After irradiation Example 1 PI-1 CBDA ODA (94), APCll- 6F (6) 38.0 17.2 20.8 Example 2 PI-2 TDA ODA (75), AMF (20), APC11-6F (5) 33.0 12.0 21.0 Example 3 PI-3 BODA DA-4P (95), APC11-6F (5) 34.4 19.7 14.7 Example 4 PI-4 PMDA ODA (94), APC18-6F (6) 37.9 29.7 8.2 Comparative Example 1 PI-5 CBDA APC18 (100) 17.7 19.5 -1.8 Comparative Example 2 PI-6 CBDA 0DA (99.4), APC11- 6F(0.6) 25.0 21.3 3.7 ※丨: The number in parentheses indicates the molar fraction of each amine in all diamines. As shown in Table 2, Examples 1 to 4 which are equivalent to the cured film obtained from the polyimide film precursor or the polyimine in the underlayer film composition for image formation of the present invention exhibit liquid repellency, The amount of change in hydrophilicity and hydrophobicity caused by ultraviolet irradiation is 8 to 21°, and the contact angle difference (5° or more) at which an image can be formed can be obtained. 0 - 46 - 201002762 In addition, the polyimine obtained from PI - 5 The film (Comparative Example 1) showed no liquid repellency. Further, the hydrophilicity was not changed by ultraviolet irradiation. On the contrary, the contact angle after ultraviolet irradiation is only slightly increased, so that an image cannot be formed. Further, the polyimine film obtained by PI-6 (Comparative Example 2) showed liquid repellency, but the amount of change in hydrophilicity and hydrophobicity caused by ultraviolet irradiation was as small as 3.7. , but can not form the contact angle difference of the image. &lt;Examples 5 to 8: Zixi t-line sensitivity characteristics (water contact angle) of a polyimide film formed of PI-1 to PI-4 &gt; PI prepared by Synthesis Example 1 to Synthesis Example 4 -1 to PI-4 solution A polyimine film was produced in the same manner as in Example 1, and the contact angle with water after irradiation with ultraviolet rays of 40 J/cm 2 was measured. The results of measurement of the water contact angle are shown in Table 3. [Table 3] r-IA 3) Water contact angle number before and after ultraviolet irradiation ----- Use PI composition without exposure 40J/cm2 Contact PI acid diamine*1 After irradiation, the angular difference PI-1 CBDA 0DA(94) , APC11-6F (6) 96.7 23.3 73.4 PI-2 TDA ODA (75), AMF (20), APC11-6F (5) 96.4 &lt;5.0 &gt; 91.4 PI-3 BODA DA-4P (95), APC11-6F ( 5) 98.5 6.8 91.7 8 PI-4 PMDA ODA (94), APC18-6F (6) 98.7 22.4 76.3: Numbers in parentheses indicate the molar fraction of each amine in all diamines. As shown in Table 3, the fifth embodiment to the eighth embodiment of the cured film obtained from the polyimine precursor or the polyimine in the film-forming underlayer film composition of the present invention -47-201002762 A large contact angle difference can be obtained by ultraviolet irradiation. That is, the underlayer film for image formation of the present invention exhibits an image forming liquid which can be used for various surface tensions. &lt;Example 9: Specific dielectric ratio of polyimine film formed by PI-2&gt; On a glass substrate with ITO (2.5 cm square 'thickness 〇.7 mm), with 0 · 2 μm A solution of the PI-2 prepared in Synthesis Example 2 was dropped onto the syringe of the pore filter, and coated by a spin coating method. Subsequently, it was heated in a hot plate at 80 ° C for 5 minutes in the atmosphere to volatilize the organic solvent, followed by heating at 1800 ° C for 60 minutes to obtain a polyimide film having a film thickness of about 40 nm. Then, in order to obtain good contact between the ITO electrode and the probe of the measuring device, one part of the polyimide film was removed to expose the ITO thick, and a vacuum vapor deposition apparatus was used to laminate the film on the polyimide film with a diameter of 1.0 mm and a film on the ITO. Aluminum electrode with a thickness of lOOnm. The vacuum vapor deposition conditions at this time were room temperature, a vacuum degree of 3×1 (T3Pa or less, and an aluminum vapor deposition rate of 33 nm/sec or less. Thus, an electrode was formed on the upper and lower sides of the polyimide film to prepare a polyimine film. The sample for electric power evaluation has a specific dielectric constant of 3 _0 for the specific dielectric constant of the polyimide film, and although the water repellency is high, it is ensured that it can be used as a gate insulating film in an organic transistor. The specific dielectric constant of 0 or more indicates that the excellent characteristics are obtained. Further, the leakage current density when the electric field MV/Cm is applied is 2x10 - 1 () A / Cm2, and it is confirmed that β 卩 is used as the gate insulation of the organic transistor. The film is absolutely -48-201002762. The edge is practically no problem. Moreover, in the present embodiment, the specific dielectric ratio of the polyimine film is determined by using AG-4311B' manufactured by Ando Electric Co., Ltd. The electrostatic capacitance was measured in a nitrogen atmosphere at a frequency of 1 KHz. The measurement of the leakage current density of the polyimine film was performed using HP4156C manufactured by AGILENT TECHNOLOGY. &lt;Comparative Example 3: by PI -5 ratio of dielectric ratio of film-forming polyimine film> except using comparative synthesis example 1 In the PI-5 solution prepared, the film was calcined at a temperature of 250 ° C for 60 minutes in a vacuum, and the film thickness was 270 nm. The same method as in Example 9 was used to evaluate the polyimide film formed by PI-5. The specific dielectric ratio of the amine film. The leakage current density of the polyimide film formed by PI-5 is lxl (T1G A/crn2 or less, but the specific dielectric ratio is 2.7. It is intended to be used as a gate insulating film). The specific dielectric constant is low, and although the performance as an underlayer film for image formation can be obtained, it cannot be used as a gate insulating film. <Synthesis Example 5> Polymerization of polyimine precursor (PI-7) in a nitrogen stream In a 100 ml 4-necked flask, OD A 1.7621 g (0.008 8 m) and APC11-6F 0.7158 g (0.0012 m) were charged, dissolved in 24.93 g of NMP, and CBDA 1.9219 g (0.0098 m) was added. This was stirred at 23 ° C for 12 hours to carry out a polymerization reaction, and further diluted with NMP to obtain 6 masses of a polyimine precursor (P 7-7). /〇 solution. -49- 201002762 The obtained polyimine precursor The number average molecular weight (?η) and the weight average molecular weight (Mw) of (PI-7) were Mn = 29, 63 0 and Mw = 67,400, respectively. &lt;Synthesis Example 6&gt; The polyimine (PI-8) was polymerized in a nitrogen stream and charged with ODA 3.4366 g (0.01716 mol), AMF 1.6151 g (0.004458 mol), APC 11.6 F 0.4176 g in a 100 ml 4-neck flask. 0.000669 mol), after dissolving in 48.65 g of NMP, 6.6927 g (0.02229 mol) of TDA was added, and the mixture was stirred at 50 ° C for 24 hours to carry out polymerization, and the obtained polyaminic acid solution was diluted to 8 mass % with NMP. To 148 g of this solution, 22.2 g of acetic anhydride and 10.3 g of pyridine were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered and dried to give a white polyimine powder. This polyimine powder was confirmed to be imidized by 90% or more by 1H-NMR. 4 g of this powder was dissolved in a mixed solvent of 3 g of γ-butyrolactone and 6 g of dipropylene glycol monomethyl ether to obtain a 10% by mass solution of polyimine (ΡΙ-8). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (?-8) were Mn = 15,300 and Mw = 31,500, respectively. &lt;Synthesis Example 7 &gt; Polyimine precursor (PI-9) was polymerized in a nitrogen stream, and placed in a 100 halo: liter 4-neck flask, loaded with ODA 3.5683 - 50 - 201002762 g (0.01782 mol), 〇_ill3g (0.00018 mol) of ι_(4_all gas octyl)phenoxy-2,4-diaminobenzene (hereinafter referred to as DA-1), dissolved in 27·99 g ΝΜΡ after 'join CBDA 3.3182 g (0.01692 mol), which was stirred at 23 ° C for 12 hours to carry out a polymerization reaction, and further diluted with hydrazine to obtain an 8 mass% solution of a polyimine precursor (PI-9). The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-9) were Mn = 31,500 and Mw = 67,200, respectively. &lt;Synthesis Example 8 &gt; Polyimine precursor (PI-10) was polymerized in a nitrogen stream, and placed in a 100 ml 4-necked flask with ODA 1.9624 g (0.0098 mol), DA- 1 0.1237 g (0·0002 mol), dissolved in 15.72 g, added CBDA 1.8434 g (0.0094 m), stirred at 23 ° C for 12 hours for polymerization, and then diluted with hydrazine to obtain poly An 8 mass% solution of the quinone imine precursor (PI-10). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-10) were Mn = 3 1,200 and Mw = 68,100, respectively. &lt;Synthesis Example 9 &gt; Polyimine (PI-1 1) was polymerized in a nitrogen stream, and placed in a 100 ml 4-necked flask, loaded with ODA 5.887 -51 - 201002762 g (0.0294 mol), DA -丨0.371 g (0.0006 mol), after dissolving 60.88 g of NMP, TDA 8.9631 g (0.03 mol) was added. The polymerization was carried out by stirring at 50 ° C for 24 hours, and the obtained polyamid NMP was diluted to 8 mass%. To 170 g of this solution, 27.8 g of acetic anhydride and 12.9 g were added as a ruthenium catalyzed catalyst, and reacted at 50 ° C for 3 hours to obtain a polyimine. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered and dried to give a white polyimine powder. This polyimine powder was confirmed to be 90% or more imidized by NMR. 4 g of this powder was dissolved in a mixed solvent of 30 g of γ-butyrolactone and 6 g of dipropylene glycol monomethyl ether to obtain a 10% by mass solution of polyimine (PI-U). The number average molecular weight (??) and weight molecular weight (Mw) of the obtained polyimine (?-11) were Mn = 30,470 and Mw = 66,900, respectively. &lt;Synthesis Example 1 0 &gt; Polyimine (pi-12) was polymerized in a nitrogen gas stream in a 1 mL-neck 4-necked flask, and charged with DA-3 8 g (0.0196 mol), DA-1 0.2473 g (0.0004 mol), after dissolving 5 6.7 g of NMP, add TDA 5.8 8 5 3 g (〇.0196 mol), disturb at 50 ° C for 24 hours into fj polymerization 'the resulting polyaminic acid solution The NMP was diluted to 8 mass%. To this solution I77 g was added 1 9.3 g of acetic anhydride, 8.9 g of the eye: for the imidization catalyst, the reaction was carried out at 50 ° C for 3 hours to obtain the poly-branched stomach, and the solution was poured into a large amount of methanol, and filtered. The white sputum solution was obtained by dry-solving the solution in a pyridine solution, and an average of 0458 solution was obtained. After drying -52-201002762, a white polyimine powder was obtained. This polyimine powder was confirmed to be imidized by more than 90% by 1 h-nmr. 4 g of this powder was dissolved in a mixed solvent of 52.67 g of γ-butyrolactone and 1 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (Ρ I - 12 ). The number average molecular weight (?n) and weight average molecular weight (Mw) of the obtained polyimine (?-1-12) were Mn = 19,700 'Mw = 47,960, respectively. &lt;Synthesis Example 1 1 &gt; Polyimine (PI-13) was polymerized in a nitrogen stream and charged with DA-3 5.1764 g (0.01261 mol) and DA-1 0.2411 g in a 100 ml 4-neck flask. (0.00039 mol), after dissolving in 3 6.77 g of NMP, add TDA 5.1 764 g (0.0 1 25 7 1 mol), stir it at 50 ° C for 24 hours to carry out polymerization, and obtain the poly-proline solution as NMP. Dilute to 8 mass%. To 130 g of this solution, 11.6 g of acetic anhydride and 5.4 g of pyridine were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered and dried to give a white polyimine powder. This polyimine powder was confirmed to be imidized by 90% or more by 1 H-NMR. 4 g of this powder was dissolved in a mixed solvent of 52.67 g of γ-butyrolactone and 1 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (Ρ 1-1 3). The number average molecular weight (?n) and weight average molecular weight (Mw) of the obtained polyimine (?1-13) were Mn = 20,970 and Mw = 51,220, respectively. -53-201002762 &lt;Comparative Synthesis Example 3 &gt; Polymerization of the polyaniline precursor (PI-14) in a nitrogen stream, in a 50 ml 4-necked flask, charged with DA-3 1. 〇 673 g (0.0026 Moer) and da- 1 0.8656 g (0.0014 mol), after dissolving in 15.31 g of NMP, adding 0.7688 g (0.00392 mol) of CBDA, stirring it at 23 °C for 12 hours for polymerization, and then diluting with NMP' A 6 mass% solution of the polyimine precursor (P1-1 4) was obtained. The number average molecular weight (?η) and the weight average molecular weight (Mw) of the obtained polyimine precursor (PI-14) were Mn = 20,1 30 and Mw = 4,28,0, respectively. The following is a list of tetracarboxylic dianhydrides and diamines used in Synthesis Example 5 to Synthesis Example 11 and Comparative Synthesis Example 3. The numerical value in the table indicates the molar fraction when the amount of the tetracarboxylic dianhydride and the diamine added is set to 1 Torr. [Table 4] (Table 4), the tetracarboxylic acid di-hepatic acid and diamine tetracarboxylic acid-dianhydride diamine CBDA TDA ODA AMF APC11-6F DA-3 DA-1 PI-7 used in the examples and comparative synthesis examples 100 88 12 PI-8 100 77 20 3 PI-9 100 99 1 PI-10 100 98 2 PI-11 100 98 2 PI-12 100 98 2 PI-13 100 97 3 PI-14 100 65 35 ※丨: Table The internal number indicates the molar fraction of each of the tetracarboxylic dianhydrides in all of the tetracarboxylic dianhydrides, or the molar fraction of each of the diamines in all of the diamines. -54-201002762 &lt;Synthesis Example 12&gt; Polyimine (PI-15) was polymerized in a nitrogen gas stream, and charged with a p-phenylenediamine of 4.86 g (0.045 mol), 1 - 74 in a 200 ml 4-necked flask.克(0.005 mol) of 4-hexadecyloxy-1,3-diaminobenzene, after dissolving in 122.5 g of NMP, adding TDA 1 5.0 1 g (0.0 5 mol), stirring at room temperature The polymerization reaction was carried out for 10 hours, and the obtained polyaminic acid solution was diluted to 8 mass% with NMP. To the solution of 50 g, 10 0 g of acetic anhydride and 5.0 g of pyridine were added as a ruthenium catalyzed catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered and dried to give a white polyimine powder. This polyimine powder was confirmed to be imidized by 90% or more by 1 H-NMR. 4 g of this powder was dissolved in a mixed solvent of 52.67 g of γ-butyrolactone and 10 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (ΡΙ-15). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (?-15) were Mn = 18,000 and Mw = 54,000, respectively. &lt;Example 1 〇: Observation of coating property change of silver fine particle dispersion (W4A) of polyimide film formed of PI-1 &gt; Glass substrate with ITO (2.5 cm square, thickness: 0.7 mm) A solution of PI-1 prepared in Synthesis Example 1 was dropped on a syringe with a 0.2 μm pore filter, and coated by a spin coating method. Then, it was heated in a hot plate at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, and then fired at -55-201002762 180 ° C for 30 minutes to obtain a polythene having a film thickness of about 4〇〇11111. Imine film. On the polyimine film, a dispersion of 3 μm of silver fine particles (product name W4A 'manufactured by Sumitomo Electric Industries Co., Ltd.) was dropped to show that the polyimide film had liquid repellency to the silver fine particle dispersion. The polyimine film obtained in the same order was irradiated with ultraviolet rays of 6 J/cm 2 irradiation, and a 3 μm silver fine particle dispersion liquid was dropped on the polyimide film to show that the polyimide film had a pro-silver dispersion. Liquid. The polyimine film obtained from Pi-1 can control the liquid-liquid lyophilic property of the silver microparticle dispersion by irradiating ultraviolet rays. &lt;Example 1 1 to Example 1 9. Comparative Example 4 to Comparative Example 6: Applicability change observation of a polyimide film formed of PI-1 to PI-3, PI-5 to PI-13 &gt Using a solution of PI-2, pi-3, PI-5 to PI-14, a polyimide film was produced in the same procedure as in Example 1, and a polyimide film was observed after irradiation with ultraviolet rays and irradiation of ultraviolet rays of 6 J/cm 2 . Liquid-repellent _ lyophilicity of silver fine particle dispersion. The results are shown in Table 5. -56 - 201002762 [Table 5] (Table 5) For the wettability change of the silver fine particle dispersion (W4A), the PI acid diamine wetness change was used. Example 10 PI-1 CBDA ODA (94), APC11-6F (6) There are Example 11 PI-2 TDA ODA (75), AMF (20), APC11-6F (5) There are Example 12 PI-3 BODA DA-4P (95), APC11-6F (5) There is Comparative Example 4 PI-5 CBDA APC18(100) Μ y ν Comparative Example 5 PI-6 CBDA ODA (99.4) &gt; APC11-6F(0.6) te j \ w Example 13 PI-7 CBDA ODA (88), APC11-6F ( 12) Example 14 PI-8 TDA ODA (77), AMF (20), APC11-6F (3) There are Example 15 PI-9 CBDA ODA (99) 'DA-1 (1) Having Example 16 PI -10 CBDA ODA(98) 'DA-1(2) Having Example 17 PI-11 TDA ODA(98) 'DA-1(2) Having Example 18 PI-12 TDA DA-3(98), DA- 1(2) There are Examples 19 PI-13 TDA DA-3 (97), DA-1 (3) Yes ※丨: The number in parentheses indicates the molar fraction of each amine in all diamines ※2: Jujuya When the amine film is irradiated with ultraviolet rays at 6 J/cm 2 , the polyilylimine film changes from a liquid-repellent property to a lyophilic property as a wet property, and the other has no change in wettability. As shown in the above Table 5, Example 1 of the cured film obtained by the polyimine precursor or the polyimine corresponding to the underlayer film composition for image formation of the present invention is irradiated to Example 19 by irradiation. Ultraviolet rays have a change in the wettability of the silver fine particle dispersion. An image can be formed by utilizing changes in wetness. On the other hand, the polyimide film (Comparative Example 4 and Comparative Example 5) obtained from PI-5 and PI-6 did not change in wettability even when irradiated with ultraviolet rays. -57-201002762 [Polymer Blend] &lt;Preparation of Composition 1 : Modulation of Underlayer Film Composition for Image Formation&gt; 6 wt% of Polyimine (PI-15) Prepared by Synthesis Example 12 8.5 g of the solution was mixed with 1.5 g of a 6 wt% solution of the polyimine (PI-12) prepared in Synthesis Example 10, and stirred at room temperature for 6 hours to obtain a composition A. &lt;Preparation Example 2 of Composition; Preparation of Underlayer Film Composition for Image Formation&gt; 9 g of a 6 wt% solution of polyimine (PI-15) prepared in Synthesis Example 12 was prepared in Synthesis Example 1 1 g of a 6 wt% solution of polyimine (PI·13) was mixed and stirred at room temperature for 6 hours to obtain a composition B. &lt;Preparation Example 3 of Composition: Preparation of Underlayer Film Composition for Image Formation&gt; 8.5 g of a 6 wt% solution of polyimine (PI-15) prepared in Synthesis Example 12 and Modification of Synthesis Example 11 15 g of a 6% solution of polyimine (?1-13) was mixed and stirred at room temperature for 6 hours to obtain a composition C. &lt;Preparation Example 4 of Composition: Preparation of Underlayer Film Composition for Image Formation&gt; 8 g of a 6 wt% solution of the polyimine (PI -1 5 ) prepared in Synthesis Example 1 and Synthesis Example 1 2 gram of a 6 wt% solution of a prepared polyimine (PI-1 3) was mixed and stirred at room temperature for 6 hours to obtain a composition D. Preparation Example 5 of the composition of the composition: Preparation of the underlayer film composition for image formation&gt; A 6 wt% solution of the polyfluorene imine (P 1 -1 5 ) prepared in Synthesis Example 1 7 · 5 g and synthesized Example 1 A 6 wt% solution of the prepared polyimine (PI-1) was mixed with 2 · 5 -58 - 201002762 g, and stirred at room temperature for 6 hours to obtain a composition E. &lt;Preparation Example 6 of Composition; Preparation of Underlayer Film Composition for Image Formation&gt; 7 g of a 6 wt% solution of polyimine (PI-15) prepared in Synthesis Example 12 was prepared by Synthesizing Example 1 3 g of a 6 wt% solution of polyimine (PI-13) was mixed and stirred at room temperature for 6 hours to obtain a composition F. &lt;Preparation of Composition 7: Preparation of Underlayer Film Composition for Image Formation&gt; 9 g of a 6 wt% solution of the polyimine (PI-15) prepared in Synthesis Example 12 and Comparative Synthesis Example 3 were prepared. 1 g of a 6 wt% solution of polyimine (PI-14) was mixed and stirred at room temperature for 6 hours to obtain a composition G. &lt;Example 20: Patterning of electrode&gt; On a glass substrate (2.5 cm square, thickness: 0.7 mm) with ΙΤ.0, the composition was dropped by a syringe with a 0.2 μm pore filter. The composition A prepared in Preparation Example 1 was applied by a spin coating method. Subsequently, in an atmosphere, the plate was heat-treated at 80 ° C for 5 minutes to volatilize the organic solvent, followed by heating at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 nm. The polyimide film was irradiated with ultraviolet rays 6 J/cm 2 through a mask. Then, a very small amount of the silver fine particle dispersion liquid is dropped onto the ultraviolet ray irradiation portion, and the lyophilic property to the ultraviolet ray irradiation portion of the polyimide film is displayed. Subsequently, the plate was fired at 180 ° C for 60 minutes to form a silver electrode having a film thickness of 50 nm. A micrograph of this silver electrode is shown in Fig. 2. -59-201002762 &lt;Example 2 1 to Example 2 7: Patternability of Electrode&gt; In addition to the use of the composition B to the composition F and the solution of PI -1 2 to PI -1 3 Example 20 The polyimine was formed into a film in the same order, and a silver fine electrode was used to form a silver electrode. All polyimide membranes can form silver electrodes with an electrode spacing of 1 μm. &lt;Comparative Example 7 &gt; A polyimine was formed in the same manner as in Example 2 except that the solution of the composition G was used, and a silver electrode was attempted to be formed using the silver fine particle dispersion. The polyimide film obtained from the solution of the composition G showed water repellency in the ultraviolet ray irradiation portion, and the desired silver electrode could not be formed (Fig. 3). &lt;Comparative Example 8 to Comparative Example 9 &gt; Polyimine was formed into a film in the same order as in Example 2 except that the PI-5 to PI-6 solution was used, and a silver electrode was attempted to be formed using the silver fine particle dispersion. The polyimine film obtained from the solution of PI - 5 to PI - 6 forms an electrode with or without ultraviolet light, and the desired silver electrode cannot be formed. -60-201002762 [Table 6] Table 6 Patterning blend ratio (mass%) of silver fine particle dispersion of the polyimide film of the present invention Electrode pattern Example 20 Composition A PI-15/PI- 12(15) Forming Example 21 Composition B PI-15/PI-13 (10) Forming Example 22 Composition C PI-15/PI-13 (15) Forming Example 23 Composition D PI- 15/PI-13(20) Forming Example 24 Composition E PI-15/PI-13 (25) Forming Example 25 Composition F PI-15/PI-13 (30) Forming Example 26 PI -12 PI-12(100) Formable Example 27 PI-13 PI-13(100) Formable Comparative Example 7 Composition G PI-15/PI-14 (10) Cannot form Comparative Example 8 PI-5 PI- 5 (100) Cannot form Comparative Example 9 PI-6 PI-6 (100) Cannot form &lt;Example 2 8 : Specific resistance ratio dielectric measurement&gt; On ITO-attached glass substrate (2_5 cm square, thickness) On 0.7 mm), the composition A prepared in the composition preparation example 1 was dropped by a syringe having a 0.2 μm pore filter, and coated by a spin coating method. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 45 nm. Next, using a vacuum vapor deposition apparatus, an in-situ electrode having a diameter of 1.0 mm to 2.0 mm and a film thickness of 100 nm was laminated on the polyimide film to prepare an insulation evaluation of the polyimide film disposed on the upper and lower sides of the polyimide film. Use the sample. The vacuum evaporation conditions at this time were room temperature, vacuum degree 3x1 (less than T3Pa, and aluminum vapor deposition rate of 0.5 nm/sec or less. -61 - 201002762) The sample was used at room temperature and humidity of 45% ± 5%. The current-voltage characteristic was measured, and a voltage was applied to the holding time of 3 seconds from the positive electrode voltage of 0 V to 80 V on the aluminum electrode side, and the current was applied to the electric field at a frequency of 1 MV/cm. The results of the measurement of the group-to-specific dielectric ratio are shown in Table 7. &lt;Example 29 to Example 35&gt; Except that the composition B was used to the composition F and the solutions of PI-12 to PI-13, Example 28 was used. The polyimide film was formed into a film in the same order, and the specific resistance and the specific dielectric constant were measured. The results are shown in Table 7. [Table 7] Table 7 Specific resistance and specific dielectric ratio of the polyimide film of the present invention (% by mass) Specific resistance (Ω cm) Specific dielectric ratio Example 28 Composition A PI-15/PI-12 (15) &gt; 1015 3.2 Example 29 Composition B PI-15/PI-13 (10) &gt;1015 3.2 Example 30 Composition C PI-15/PI-13(15) &gt; 1015 3.2 Example 31 Composition D PI-15/PI-13(20) &gt; 1015 3.2 Example 32 Composition E PI-15/PI-13(25) &gt;1 015 3.1 Example 33 Composition F PI-15/PI-13 (30) &gt; 1015 3.1 Example 34 PI-12 PI-12 (100) &gt; 1015 3 Example 35 PI-13 PI-13 (100) &gt;1015 3 &lt;Example 3 6: Preparation of organic transistor&gt; On the silver electrode obtained in Example 20, poly(3-hexylthiophene-2,5-diyl) was adjusted (obtained by MERCK, after The abbreviated as P3HT) is a coating solution of P 3 HT dissolved in xylene at a concentration of 2% by mass to 62-201002762, and is subjected to a spin coating method on the polyimine film at an oxygen concentration of 5.5 ppm or less. The coating solution was applied under a nitrogen atmosphere. Subsequently, in order to completely evaporate the solvent, the semiconductor layer was formed by heat treatment at 1 Torr for 60 minutes under vacuum to complete the organic thin film transistor. The organic thin film transistor obtained above was obtained. The electrical characteristics are evaluated by measuring the change in the gate current of the gate voltage. In detail, 'the source-drain voltage (VD) is set to -40V, and the gate voltage (VG) is from +30V to - 30V, each 2V step change, after the current is very stable, hold the voltage for 1 second, and then measure it as the drain current and record it. Using a semiconductor parameter analyzer HP4156C (AGILENT TECHNOLOGY (shares)) was performed. When the gate voltage is applied to the negative erbium, a large increase in the drain current is observed, and it is confirmed that P3HT can function as a p-type semiconductor (Fig. 4). Next, the relationship between the source current and the source voltage when the gate voltage (VG) was changed from +20 V to -30 V in steps of 10 V was measured to confirm that the organic transistor normally functions (Fig. 5). Generally, the drain current Id in the saturated state can be expressed by the following equation. That is, the mobility V of the organic semiconductor can be obtained by plotting the square root of the absolute 値 of the drain current 1D as the vertical axis and the slope when the gate voltage V G is plotted as the horizontal axis.

ID = WCp(VG-VT)2/2L -63- 201002762 In the above formula, 'W is the channel width of the transistor, L is the channel length of the transistor' C is the electrostatic capacitance of the gate insulating film, and VT is the transistor Threshold 値 voltage, μ is mobility. The P3HT mobility/z is 2xl (T13 cm2/Vs) and the 'threshold voltage is 16V. The ratio of the on state to the off state (on/off) is 1 02 (Table 8). 'The electrical properties of the organic thin film transistor are affected by the removal of the surrounding humidity and the active material. Therefore, after the component is completed, it is moved to the vacuum as soon as possible (the vacuum degree is 5xl (below T2Pa). After leaving for about 30 minutes, the vacuum is kept at 5x. l (Measured by T2Pa or less. &lt;Example 37: Organic transistor&gt; An organic transistor was produced in the same manner as in Example 36 except that the silver electrode obtained in Example 21 was used. &lt;Example 38 : Organic transistor > An organic transistor was produced in the same manner as in Example 36 except that the silver electrode obtained in Example 27 was used. [Table 8] Table 8 Example 3 6 to 3 8 Phase blend ratio (% by mass) Mobility (cm2/Vs) On/off ratio Vt(V) Example 36 Composition A PI-15/PI-12(15) 2xl〇·3 &gt; 102 16 Example 37 Composition B PI-15/PI-13(10) 2x1 (Γ3 &gt; 102 15 Example 38 PI-13 PI-13(100) 3x1 Ο·3 &gt;102 19 -64- 20100 2762 The polyimine of the present invention can be patterned by using the difference in hydrophilicity and hydrophobicity to show that an organic transistor having a channel length of 1 μm can be produced. Further, it exhibits high insulation of 1015 〇cm or more and 3.0 or more. The specific dielectric ratio can be used not only as an underlayer film for image formation but also as a high performance as a gate insulating film for an organic transistor. From the above results, it is shown to be a precursor of a polyfluorene containing a fluorine-containing alkyl group. And the cured film obtained from the underlayer film composition for image formation of the present invention obtained from the polyimine imide obtained from the polyimine precursor, which has a high water repellency and a high specific dielectric ratio, and thus Fig. 1 is a schematic cross-sectional view showing the structure of an organic transistor having an underlayer film for image formation of the present invention. Fig. 2 is a view showing a silver microparticle obtained in Example 20. Fig. 3 is a pictorial example of the silver fine particle dispersion obtained in Comparative Example 7. Fig. 4 is a view showing the polyimine film obtained from the composition A as an image in Example 36. Forming the bottom layer and the gate insulating film Graph of the relationship between the drain current (Drain Current) and the gate voltage of the organic transistor. Fig. 5 shows that the polyimide film obtained from the composition A is also used for image formation in Example 36. A graph of the relationship between the drain current (Drain Current) and the drain voltage of the organic transistor of the bottom layer and the gate insulating film. -65- 201002762 [Description of main component symbols] 1 : Substrate 2 : Gate electrode 3 : Also used as an underlying film gate insulating film for electrode formation 4: Source electrode, drain electrode 5 : Semiconductor layer -66 -

Claims (1)

201002762 VII. Patent application scope: 1. An underlayer film composition for image formation characterized by containing a polyimine precursor having a structural unit represented by the following formulas (1) and (la) and the polyazide At least one compound selected from the group consisting of polyazonia obtained by dehydration ring closure of an amine precursor: [Chemical 1] /r1OOC COOR2 \ /R1»OOC COOR28 \ TO sT61! (1) (1a) A represents a tetravalent organic group, B1 represents at least one divalent organic group represented by the following formula (2), B2 represents a divalent organic group, and R1, R2, Rla, and R2a each independently represent a hydrogen atom or a monovalent organic group. The total number of moles of the structural unit represented by the formula (1) 'm is the total number of moles of the structural unit represented by the formula (1a), and n and m respectively represent a positive integer and satisfy 0.01 Sn/(n + m) S 0.3) [Chemical 2] 々Xl, xrR3 (2) (where Χι denotes a single bond, -〇-, -co〇-, -〇c〇-, -C0NH_, _ch2〇-, X2 represents a carbon number of 3 To a bis-valent organic group of 18, R3 represents a perfluoroalkyl group having 2 to 12 carbon atoms. In the above formula (la), 'B2 is at least one selected from the group consisting of the following formulas (3) to (5), in the above formula (la), wherein the 'B2 is at least one selected from the group consisting of the following formulas (3) to (5). One: (wherein Y1 independently represents a single bond, an ether bond, an ester bond, a sulfur ugly bond, a stilbene bond, a pendant group having a branched structure of 1 to 3 carbon atoms, or a carbon number of 1 to 3) The alkylene dioxyl group having a branched structure represents a single bond, an ether bond, an ester bond, a thioether bond, or a guanamine bond, and the r4 group has a hydrogen atom alone, a methyl group, an ethyl group, a trifluoromethyl group, and a R5 group. Represents a hydrogen atom, a methyl group, a monofluoromethyl group, R6 represents a methyl group, a stretched ethyl group, and j is a single 31. represents a ruthenium or a 1) group formed by an underlying film group of a tetravalent organic group: 3 An image of the first or second aspect of the patent, wherein in the above formulas (1) and (la), "A" is at least selected from the group consisting of the following formulas (6) to (1 1) [ 4] (6) t (Formula - for the trial, fluorine atom or R7, R8, R9, R1G independently of the original -68- 201002762 hydrocarbon number of 1 to 4). The primer film composition for image formation according to any one of claims 1 to 3, which comprises a polyimine precursor having a structural unit represented by the above formula (1) and formula (la) and The polyimine obtained by subjecting the polyimine precursor to dehydration ring closure is obtained by reacting a tetracarboxylic dianhydride represented by the following formula (16) with a diamine represented by the following formulas (17) and (18). Yttrium imide precursor and polyimine: H2n-b2-nh2 &lt;18) (wherein A, B1 and B2 are the same as defined in the above formulas (1) and (la)). An underlayer film for image formation, which is obtained by using the underlayer film composition for image formation according to any one of claims 1 to 4. An underlayer film for forming an electrode pattern, which is obtained by using the underlayer film composition for image formation according to any one of claims 1 to 4. 7. A gate insulating film for an organic transistor, which is obtained by using the underlayer film composition for image formation according to any one of claims 1 to 4. 8 · An organic transistor, which is obtained by using a gate insulating film for an organic transistor of the seventh application of the patent application. -69-