TWI453235B - Underlayer film for forming image - Google Patents

Description

Underlayer film

The present invention relates to an underlayer film for forming an image, and further relates to an organic transistor produced by using a film formed under the image.

At present, in the manufacturing steps of the electronic device, a mask evaporation method or an etching method using photolithography is mainly used for forming a pattern of an electrode or a functional film. These conventional methods have been pointed out to be problematic in that the size of the substrate is large and the steps are complicated.

In recent years, for such conventional methods, a separate coating technique utilizing the difference in liquid wettability has been proposed for use in the patterning of functional films. This is to form a patterned layer on the surface of the board which is composed of a field in which the liquid is easily wetted and which is not easily wetted by the liquid. Then, a solution forming the functional film material is applied onto the patterned layer. A method of producing an electronic device such as an organic EL (electroluminescence) device or an organic FET (electric field effect transistor) device by drying a functional film only in the field where the liquid is easily wetted.

It is known that the patterned layer for the functional film is irradiated with ultraviolet light through a photocatalyst layer composed of titanium oxide and an organic polysiloxane (for example, refer to Patent Document 1), for dyes, and the like. The compound having the light absorbing portion and the fluoropolymer are irradiated with a laser or transmitted through a mask to irradiate ultraviolet light (see, for example, Patent Document 2). Further, a method of forming the above-described patterned layer by vapor deposition of a fluorine-based coating agent is also proposed (for example, see Patent Document 3).

The patterning layer proposed so far in the above-mentioned patent documents and the like only achieves the role of patterning of the functional film, but remains in the element. Therefore, the patterned layer is necessary for the durability of the subsequent steps and the reliability of the electronic device without adversely affecting its characteristics. These necessary characteristics of the patterned layer differ depending on the pattern used or the location of the patterned layer, wherein the electrical insulation of the patterned layer of the electrode is an important characteristic.

Moreover, the method proposed so far only focuses on the characteristics of the graphical layer. Therefore, for example, when the source electrode and the drain electrode of the organic FET device are patterned, it is necessary to separately prepare a gate insulating film under the patterned layer.

On the other hand, polyimine is excellent in heat resistance, mechanical strength, electrical insulation, chemical resistance, and the like, and has been used in various electronic devices. The use of polyimine as a patterning layer has been disclosed using a tetracarboxylic anhydride having an alicyclic structure (for example, refer to Patent Document 4). However, in such cases, since the amount of irradiation of ultraviolet rays is extremely large, it is necessary to perform long-time exposure processing.

Patent Document 1: JP-A-2000-223270

Patent Document 2: JP-A-2004-146478

Patent Document 3: JP-A-2004-273851

Patent Document 4: JP-A-2006-185898

The present invention has been made in view of the above circumstances, and the present invention provides an underlayer film for forming an image which can easily change the hydrophilicity of the formed film surface of the underlayer film for image formation even with a small amount of ultraviolet irradiation.

[Means to solve the problem]

As a result of repeating the positive review for achieving the above object, the present inventors have found that the thiol ester structure is contained in the side chain of the polyimine imide obtained from the polyimide or the polyimide precursor. On the surface of the cured film obtained from the polyimide precursor and the polyimide, the contact angle of the water can be made small by a small amount of exposure, and thus the present invention has been completed.

That is, the first aspect of the present invention relates to an underlayer film for forming an image characterized by containing a polyimine precursor having a repetitive structure represented by the following formula (1) or dehydrating the polyimine precursor. The resulting polyimine:

(wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2) or (3), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents a natural number) ;

(wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or An alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

The second aspect of the present invention relates to an underlayer film for forming an image, which comprises a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and containing the formula (7). The polyimine precursor obtained by reacting the diamine component of the diamine, or the polyimine obtained by dehydrating and ring-closing the polyimine precursor:

H ₂ N-B-NH ₂ (7)

Wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or formula (3):

(wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or An alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3)].

The third aspect relates to the underlayer film for forming an image according to the first or second aspect, wherein Z of the formula (2) or the formula (3) represents an aliphatic group having 3 to 26 carbon atoms substituted by a fluorine atom of any hydrogen atom. Hydrocarbyl group.

The fourth aspect relates to an underlayer film for forming an image described in the first to third aspects, wherein A represents a tetravalent organic group having an aliphatic ring or only an aliphatic group.

The fifth aspect relates to the underlayer film for forming an image described in any one of the first to fourth aspects, wherein B represents a divalent structure represented by the formula (2).

The sixth aspect is the lower layer film for forming an image according to any one of the first to fifth aspects, wherein X and Y represent a single bond.

The seventh aspect relates to an organic transistor characterized by comprising the underlayer film formed as described in any one of the first to sixth aspects.

The eighth aspect relates to a diamine compound represented by the following formula (14) or the following formula (15),

(wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, and R each independently represents a fluorine atom and an alkyl group having 1 to 3 carbon atoms. An oxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

The ninth aspect relates to a polyimine which contains a polyimine precursor which is a repeating unit represented by the following formula (1) or which is obtained by dehydrating and ring-closing the polyimine precursor.

(wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2a) or (3a), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents a natural number) ;

(wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, and R each independently represents a fluorine atom and an alkyl group having 1 to 3 carbon atoms. An oxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

The tenth aspect relates to a method for forming an image forming film of a lower layer, comprising a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and containing the formula (7). The polyimine precursor obtained by reacting the amine diamine component or the polyimine obtained by dehydrating and ring-closing the polyimine precursor:

H ₂ N-B-NH ₂ (7)

(wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or formula (3):

R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-. , -CONH-, -CH ₂ O-, -CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R independently represents a fluorine atom, An alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

The eleventh aspect is the lower layer film coating liquid for forming an image according to the tenth aspect, wherein the Z of the formula (2) or the formula (3) represents a fat having 3 to 26 carbon atoms in which any hydrogen atom is replaced by a fluorine atom. A hydrocarbon group.

The twelfth aspect is the image forming underlayer film coating liquid according to the tenth aspect or the eleventh aspect, which further comprises a soluble polyimine having a ruthenium iodide ratio of 80% or more.

The thirteenth aspect relates to a layer film for forming an image, which is characterized in that the tenth aspect is the formation of the image forming underlayer film coating liquid described in the twelfth aspect.

The fourteenth aspect relates to an organic transistor characterized by having a film obtained by firing the formed underlayer film coating liquid described in the tenth to thirteenth aspects.

[Effect of the invention]

In the lower layer film for forming an image of the present invention, the surface of the film can be changed from hydrophobic to hydrophilic by a small amount of ultraviolet irradiation, and accordingly, an image of a functional material such as an electrode can be formed by using the property. Therefore, the step time in the manufacture of the electronic device can be greatly shortened, and it becomes a material which is quite effective in terms of productivity.

The present invention relates to a novel formation underlayer film comprising a polyimine imide obtained from a polythioimine precursor having a thiol ester bond in a side chain or the polyimine precursor. Further, the present invention relates to an organic transistor using the above-described film forming an image.

[Polyimine precursor] The present invention is an underlayer film for forming an image, which is characterized in that it contains a polyimine precursor having a repetitive structure represented by the following formula (1) or dehydration of the polyimine precursor. The resulting polyimine:

(wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2) or (3), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents a natural number) .

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and specific examples of the monovalent organic group are, for example, an alkyl group having 1 to 4 carbon atoms.

The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group.

Among them, R ¹ and R ^{2 are} preferably a hydrogen atom.

In the above formula (1), the structure of the organic group represented by A is not particularly limited as long as it is a tetravalent organic group. Further, the polyimine precursor may have one or a plurality of structures represented by the formula (1). Therefore, in the polyimine precursor, the structure of the organic group represented by A may be one type, or a plurality of kinds may be mixed. Wherein A is preferably a tetravalent organic group having an aliphatic ring or only an aliphatic group. More preferably, it is a tetravalent organic group having an aliphatic ring.

Preferred specific examples of the organic group represented by A are exemplified by the organic groups of the following formulae A-1 to A-46.

When the above formulae A-1 to A-46 are used as the underlayer film for forming an image, they can be appropriately selected depending on the desired characteristics.

For example, in the above formulas A-1 to A-46, as a tetravalent organic group for improving the exposure sensitivity (in the present specification, the exposure sensitivity indicates the degree of self-hydrophobicity per hydrophilic amount of ultraviolet light irradiation) Listed as the tetravalent organic group having an aliphatic ring or an aliphatic group of the formulae A-1 to A-25, the most effective organic group is listed as A-1, A-6, A-16 or A-19. .

Further, the tetravalent organic group of the formulae A-1 to A-25 is also preferable from the viewpoint of improving the insulating effect.

In the above formula (1), in the organic group represented by A, when the group other than the formula A-1 to A-25 is mixed, the ratio of the formulae A-1 to A-25 is preferably 10 mol% or more, more preferably It is 50 mol% or more, preferably 80 mol% or more.

In the above formula (1), B represents a divalent structure having a thiol ester bond in a side chain represented by the following formula (2) or formula (3).

By the thiol bond on the side chain of the polyimine precursor containing the repetitive structure represented by the formula (1) (or the polyimine thus obtained), when the thiol ester group is photodecomposed, The side chain of the thiol ester linkage will be cleaved from the polymer backbone. Therefore, by adjusting the hydrophilicity and hydrophobicity of the side chain bonded through the thiol bond, it is expected that the hydrophilicity and the like are changed by irradiation with light such as ultraviolet rays.

In the above formula (2) or (3), X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms.

Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CH ₂ COO- or -CH ₂ CH ₂ COO-.

Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms, and any hydrogen atom may be substituted with a fluorine atom.

R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

In the structure of B represented by the above formula (2) or (3), an aromatic carbon ring may be contained in the side chain structure from the viewpoint of improving the absorption efficiency of ultraviolet rays.

Therefore, in the above formula (2) or (3), when X represents a divalent aromatic group having 6 to 20 carbon atoms, preferred aromatic groups are phenyl, biphenyl, terphenyl, and naphthene. Base, stretch base, etc.

The aliphatic hydrocarbon group having 3 to 26 carbon atoms in the above Z is exemplified by propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, a linear or branched alkyl group of a fluorenyl group, a second fluorenyl group, an isodecyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group; an allyl group Alkenyl group such as alkenyl group; alicyclic hydrocarbon group having cyclobutane, cyclopentane, cyclohexane, cyclodecane, steroid skeleton, adamantane or the like; ethyl formate, methyl acetate, ethyl acetate, propionic acid Methyl ester, diacetyl, methyl isobutyrate, ethyl isobutyrate, ethyl butyrate, propyl butyrate, isobutyl acetate, isobutyl isobutyrate, isobutyl butyrate , isobutyl isovalerate, isoamyl acetate, isoamyl propionate, pentyl propionate, amyl isobutyrate, amyl butyrate, amyl isovalerate, allyl hexanoate, acetyl Ethyl acetate, ethyl heptanoate, heptyl acetate, ethyl octanoate, stearyl acetate, decyl acetate, borneol acetate, ester of diethyl phthalate, etc., preferably having a carbon number of 12 to 26 a linear alkyl group.

Any hydrogen atom of the above aliphatic hydrocarbon group may be substituted by a fluorine atom, preferably an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, preferably a linear fluorine having 4 to 7 carbon atoms. alkyl.

Preferred specific examples of the B structure represented by the above formula (2) or (3) are as shown in the following structures [B-1] to [B-17]. Among these divalent structures, from the viewpoint of easy improvement in hydrophobicity, it is preferably a divalent structure represented by [B-13] to [B-17], and more preferably [B-15] to [B-17] indicates a two-valent structure.

Further, in consideration of other characteristics, such as insulating properties, solvent solubility, film formability, and further adhesion of the film, the polyimine precursor used in the underlayer film for forming an image of the present invention ( And the polyimine obtained therefrom may be in addition to the structure represented by the above formula (1), and the divalent organic group B in the above formula (1) may be substituted to have no thiol ester bond in the side chain. The polyvalent imine precursor of the other divalent organic group D represented by the following formula (4) (and the polyimine obtained therefrom).

In this case, the structure represented by the above formula (1) and the other divalent organic group having no thiol ester bond in the side chain are contained in the divalent organic group B having a thiol ester bond in the side chain ( 4) The bond of the structure may be any of block bonding and/or random bonding.

In the formula, A, R ¹ and R ² are the same as defined in the above formula (1), m represents a natural number, and D represents another divalent structure having no thiol ester bond in the side chain.

In the polyimine precursor (and the polyimine obtained therefrom) used in the formation of the underlayer film of the present invention, in the formula (4), when D is a long-chain alkyl group in the side chain, excessive Increasing the content ratio of the structure represented by the formula (4) (the structure having no thiol ester bond in the side chain) will lower the sensitivity to ultraviolet rays. According to this, when the structure represented by the formula (4) is contained, the ratio of the structure represented by the formula (1) (structure having a thiol ester bond in the side chain) is preferably 30 mol% or more.

Moreover, in order to further improve the exposure sensitivity and shorten the irradiation time of the ultraviolet rays, it is necessary to further increase the content ratio of the structure represented by the formula (1), and the content ratio in this case is preferably 50 mol% or more.

Further, in the formula (4), when D does not have a long-chain alkyl group in the side chain, since the hydrophobicity of the film is mainly affected by the ratio of the structure represented by the formula (1), the surface tension of the image forming liquid or the upper layer is considered. The ratio of the structure represented by the formula (1) may be determined by the adhesion of the member or the like.

Further, in the structure represented by the above formula (2) or (3), when one part of the aliphatic hydrocarbon group of Z is substituted by a fluorine atom, the ratio of the structure represented by the formula (1) is 10 mol% or less. High hydrophobicity and sensitivity can also be obtained. That is, it is considered that the change in the hydrophilicity of the film is caused by the decomposition of the side chain structure, and the exposure sensitivity is not necessarily lowered when the ratio of the formula (1) is 10 mol% or less.

In the above formula (4), the other divalent structure D having no thiol ester bond is preferably a structure having high insulating properties, and specifically, the following [D-1] to [D-57] are mentioned. Construction.

In the following [D-1] to [D-57], the structure of [D-1] to [D-5] is preferable from the viewpoint of improving the ease of insulation.

Further, the structures having a high solvent solubility improving effect are listed as [D-2], [D-5], [D-7], [D-8], [D-12], [D-22], [ D-24] to [D-27], [D-29].

Further, specific examples of the hydrophobic structure having a long-chain alkyl group in the side chain include the structures of [D-55] to [D-27], but as the characteristics of the organic transistor, improvement in insulation can be expected. Use within the range of not reducing the sensitivity, such use should pay attention to the proportion of use.

The polyimine precursor is produced by, for example, polymerizing a tetracarboxylic dianhydride and a derivative thereof with a diamine. In particular, the polyimine precursor (polylysine) represented by the following formula (5) is preferred because the tetracarboxylic anhydride component and the diamine component are relatively simple to react.

(wherein, A, B and n are the same as defined in the formula (1)).

"Tetracarboxylic dianhydride and its derivatives"

In the present invention, the tetracarboxylic dianhydride and the derivative thereof are not particularly limited, but a tetracarboxylic dianhydride represented by the following formula (6) is preferably used. A in the formula is the same as defined in the above formula (1), and specific examples thereof are as shown in the above formulas A-1 to A-46.

(wherein A is the same as defined in the formula (1)).

As described so far, in the polyimine precursor, the structure of the organic group represented by A may be one type, and a plurality of kinds may be mixed. Wherein A is preferably a tetravalent organic group having an aliphatic ring or only an aliphatic group, more preferably a tetravalent organic group having an aliphatic ring. Accordingly, the tetracarboxylic dianhydride component preferably contains a large amount of a compound of the formula (6) having an aliphatic ring or a tetravalent organic group composed only of an aliphatic group. More preferably, a compound of the formula (6) containing a large amount of A as a tetravalent organic group having an aliphatic ring is preferred.

When a polyimine precursor or the like is produced using only the aromatic acid dianhydride, the insulating film is remarkably lowered when a high electric field is applied to the underlayer film for forming an image. On the contrary, when an aliphatic acid dianhydride is used, it is excellent in insulation in a high electric field.

For example, when the operating voltage of the organic transistor is about 1 MV/cm, in the case of the use, it is preferable to use a fatty acid dianhydride as a raw material of the polyimide precursor in view of the insulating property.

Diamine

In the present invention, the diamine used in the diamine component is represented by the following formula (7), and B is a structure represented by the following formula (2) or the following formula (3), that is, having a mercaptan in the side chain. The divalent structure of the ester bond. Specific examples of B are as shown in the above [B-1] to [B-17].

[Chem. 24]

H ₂ N-B-NH ₂ (7)

(wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or An alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

Further, in addition to the diamine represented by the formula (7), a diamine other than the formula (7) represented by the formula (Q1) may be used in the range in which the effects of the present invention are exhibited.

[Chem. 26]

H ₂ N-D-NH ₂ (Q1)

In the formula (Q1), D is the same as defined in the above formula (4). According to this, a specific example of the diamine represented by the formula (Q1) is a diamine having a divalent structure represented by the above [D-1] to [D-57].

[Synthesis method of diamine compound]

Among the diamines represented by the above formula (7), a method of obtaining a diamine having a structure of the formula (2) is not particularly limited. When it is shown by an example, the dinitro compound represented by the following general formula (8) is synthesized, and the nitro group is converted into an amine group. The method for reducing the dinitro compound is not particularly limited, and palladium-carbon, platinum oxide, nickel iridium, iron, tin chloride, platinum black, lanthanum-alumina or the like is usually used as a catalyst, and ethyl acetate, toluene, and the like are used. A method in which a solvent such as tetrahydrofuran, dioxane or an alcohol is reacted with hydrogen, hydrazine, hydrogen chloride or ammonium chloride. In the present invention, a compound having a sulfur atom or the like in the skeleton of the dinitro compound may occasionally become a catalytic agent, and may inactivate the catalyst. Therefore, it is more preferable to use nickel, iron, tin chloride, or the like. Chemical reduction method.

(wherein, X, Y, Z, R and t are the same as defined in the above formula (2)).

The dinitro compound of the above formula (8) can be obtained by reacting dinitrobenzhydryl chloride (9) shown below with a compound (10) containing a thiol group.

(wherein, X, Y, Z, R and t are the same as defined in the above formula (2)).

Among the diamines represented by the above formula (7), a method of obtaining a diamine having a structure of the formula (3) is not particularly limited. For example, a dinitro compound represented by the following formula (11) can be synthesized, and then obtained by reductively converting a nitro group into an amine group as in the case of the above dinitro compound (8).

(wherein, X, Y, Z, R and t are the same as defined in the above formula (3)).

The dinitro compound of the above formula (11) can be reacted with a thiol group-containing dinitro compound (12) shown below and a ruthenium chloride (13) having an aliphatic hydrocarbon which may also contain a fluorine atom. obtain.

(wherein, X, Y, Z, R and t are the same as defined in the above formula (3)).

"Manufacturing method of polyimine precursors"

In the case of obtaining a polyimine precursor having a repeating structure represented by the formula (1), a tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the above formula (6) and containing the above formula (7) The method of mixing and reacting the diamine represented by the diamine component represented by the above formula (Q1) in an organic solvent as needed is a simple method.

A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent is exemplified by stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and directly adding or dispersing a tetracarboxylic dianhydride. Or a method of adding in an organic solvent; instead, a diamine component is added to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent; and a tetracarboxylic dianhydride component and a diamine component are alternately added. Method, etc.

Further, in the case where the tetracarboxylic dianhydride component and the diamine component are in a plurality of compounds, the polymerization reaction may be carried out in a state in which the plurality of components are mixed in advance, or the polymerization reaction may be carried out in an orderly manner.

When the polyimine precursor used in the present invention is polymerized, the ratio of the tetracarboxylic dianhydride component to the diamine component, that is, the total molar amount of the tetracarboxylic dianhydride component: (diamine component) The total molar number is preferably from 1:0.5 to 1:1.5. As with the usual polymerization reaction, the closer the molar ratio is to 1:1, the greater the degree of polymerization of the polyimine precursor formed, and the molecular weight increases.

In the method for producing a polyimine precursor, the temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted in an organic solvent is usually -20 to 150 ° C, preferably 0 to 80 ° C.

When the reaction temperature is set to a high temperature, the polymerization reaction proceeds rapidly and is completed, but when it is too high, a high molecular weight polyimine precursor cannot be obtained.

Further, when the polymerization reaction is carried out in an organic solvent, the solid content concentration of the two components (the total mass of the tetracarboxylic anhydride component and the diamine component) in the solvent is not particularly limited, but it is difficult to obtain a high molecular weight polyfluorene when the concentration is too low. In the imine precursor, when the concentration is too high, the viscosity of the reaction liquid is too high to be uniformly stirred, so it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. It may be carried out at a high concentration in the initial stage of the polymerization, and then an organic solvent may be added together with the purification of the polymer (polyimine precursor).

The organic solvent to be used in the above-mentioned polymerization reaction is not particularly limited as long as it is a polyimine precursor which can be dissolved, but specific examples thereof include N,N-dimethylformamide and N. , N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl Kea, γ-butyrolactone and the like. These may be used singly or in combination of two or more. Further, even a solvent in which the polyimide intermediate precursor cannot be dissolved may be mixed in the solvent as long as it does not precipitate the formed polyimide precursor.

The solution containing the polyimine precursor thus obtained can be used as it is in the formation of a film coating liquid under the image. Further, the polyimide precursor may be precipitated and recovered in a weak solvent such as water, methanol or ethanol, and recovered.

[polyimine]

The polyimine precursor having a structure represented by the above formulas (1) and (4) (and the above formula (5)) can be subjected to dehydration ring closure to form a polyimine. The method for the ruthenium imidization reaction is not particularly limited, but the imidization of a catalyzed ruthenium using a basic catalyst and an acid anhydride is less likely to cause a decrease in the molecular weight of the quinone imine during the ruthenium imidization reaction, and the ruthenium imidization The control of the rate is easier and better.

The catalyst imidization can be carried out by stirring the aforementioned polyimine precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 100 hours.

Further, the polyimine precursor may be directly (unalone) a solution containing a polyimide precursor obtained by polymerization of the above tetracarboxylic anhydride component and a diamine component.

The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity in carrying out the reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because it is easier to purify the polyimine obtained after the ruthenium imidization.

As the organic solvent, a solvent used in the polymerization of the above polyimine precursor can be used.

The reaction temperature in the imidization of the catalyst oxime 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 will proceed rapidly, but when it is too high, the molecular weight of the polyimine will decrease.

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 polyimine precursor. Further, the amount of the acid anhydride is from 1 to 50 moles, more preferably from 3 to 30 moles, relative to the acid amide group in the aforementioned polyimide intermediate.

By adjusting the above reaction temperature and the amount of the catalyst, the yield of the obtained ruthenium imine can be controlled.

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, but since the reaction solution contains a ruthenium-based catalyst, it is preferred to use a polyimide reaction. Purification ‧ Recycling ‧ Washers

A convenient method for recovering polyimine is to pour the reaction solution into a weak solvent under stirring to precipitate the polyimine and filter it.

The weak solvent to be used at this time is not particularly limited, and may, for example, be methanol, hexane, heptane, ethanol, toluene, water or the like. After the precipitate is recovered by filtration, it is preferably washed with the above weak solvent.

The recovered polyimine can be dried to a polyimine powder at normal temperature or under reduced pressure under normal pressure or reduced pressure.

The polyimine powder is further dissolved in a good solvent, and reprecipitation is repeated in a weak solvent for 2 to 10 times, and impurities in the polymer can be further reduced.

The good solvent to be used at this time is not particularly limited as long as it is a soluble polyimide precursor or polyimine, but examples thereof are, for example, N,N-dimethylformamide, N,N-dimethyl Acetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methyl caprolactone Amine, dimethyl hydrazine, tetramethyl urea, pyridine, γ-butyrolactone and the like.

Further, when three or more kinds of weak solvents such as alcohols, ketones, and hydrocarbons are used as the weak solvent used in the re-sinking chamber, the purification efficiency can be further improved.

[Formation of film coating liquid under the image]

The underlayer film for forming an image of the present invention can be formed by forming a film coating liquid under the image. The film coating liquid under the formation of the image may be a coating liquid containing the above-mentioned polyimide precursor, the above-mentioned polyimine, and a solvent, and if necessary, a coupling agent or a surfactant which will be further described, It is preferred to contain a polyfluorene imine precursor obtained by reacting a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine component containing a diamine represented by the formula (7). Or a coating liquid of the polyimine obtained by subjecting the polyimine precursor to dehydration ring closure.

H ₂ N-B-NH ₂ (7)

(wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or (3),

R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-. , -CONH-, -CH ₂ O-, -CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom An alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3.

It is preferable that the Z of the above formula (2) or (3) represents a layered film coating liquid which is formed by forming an aliphatic hydrocarbon group having 3 to 26 carbon atoms which is substituted with a fluorine atom.

The molecular weight of the polyimine precursor and/or polyimine used in the film coating liquid formed in the image forming layer described above is from the viewpoints of ease of handling and solvent resistance at the time of film formation. The weight average molecular weight (result as measured by GPC) in terms of polyethylene glycol (or polyethylene oxide) is preferably 2,000 to 200,000, more preferably 5,000 to 50,000.

When the underlayer film for forming an image is formed by using the above-mentioned underlayer film coating liquid for forming an image, and the ultraviolet ray is irradiated, the amount of change in the hydrophobicity is not greatly different between the polyimine precursor and the polyimine. Therefore, when the underlayer film for forming an image is focused on this point, the yield of hydrazine imidation is not particularly limited.

However, by using polyimide, it is possible to obtain a highly reliable film which can be fired at a low temperature (180 ° C or lower) which is compatible with a plastic substrate, since the polyimide is more than a polyimide precursor. Since the polarity is low, the advantage of improving the water contact angle before ultraviolet irradiation (which can improve the hydrophobicity) can be obtained, so that it is more preferable to use polyimine.

On the other hand, when the underlayer film coating liquid is formed in the underlayer film (for example, a gate insulating film) which is mainly used for forming an insulating layer, the coating solution has a yttrium imidation ratio of preferably 90%. the above. However, the ruthenium imidization ratio can be lowered without impairing the solvent solubility. However, in this case, when the film is formed, the lowermost layer is made into a high-yield imidization by using a blending method described later (high insulation). It is useful to retain high insulation as a lower film.

The solvent used in the above-mentioned layer forming film coating liquid is not particularly limited as long as it is a soluble polyimide precursor or a polyimide, and examples thereof are N,N-dimethylformamide. N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, A good solvent such as N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine or γ-butyrolactone. These may be used singly or in combination, and a weak solvent such as an alcohol, a ketone or a hydrocarbon may be used in combination with the above-mentioned good solvent.

The ratio of the solid content in the layer coating liquid to be formed in the image formation layer is not particularly limited as long as the components including the coupling agent to be described later are uniformly dissolved in the solvent, and are, for example, 1 to 30% by mass, for example, 5 Up to 20% by mass. Here, the solid content means that the solvent is removed from all the components of the layer coating liquid under the formation image.

The method for preparing the layer coating liquid under the formation of the image is not particularly limited, but a solution containing the polyimine precursor obtained by polymerization of the tetracarboxylic anhydride component and the diamine component described above may be used as it is, or The reaction solution of the polyimine obtained by the solution.

Moreover, in order to improve the adhesiveness of this coating liquid and a board|substrate in the coating film formation liquid below the image formation, the coupling agent may further be contained, in order to not damage the effect of this invention.

The coupling 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, 3-aminopropyltriethoxydecane, and 2 -Aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-amine Benzyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3 -Aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-trimethoxydecylpropyltriethylamine, N-triethoxy Base alkyl propyl triethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triaza Decane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl 3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl- 3- Propyltriethoxydecane, N-bis(oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3-aminopropyltriethoxy Decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 6-tetraglycidyl-2,4-hexanediol, N, N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N', A compound such as N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

These may be used alone or in combination of two or more.

When the coupling agent is used, the content thereof is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the film coating liquid under the formation of the image.

Further, in the layer coating liquid for forming the image, the surfactant may be contained in order to improve the coating property of the coating liquid, the film thickness uniformity or the surface flatness of the film obtained from the coating liquid.

The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. Such surfactants are listed, for example, as F TO PEF 301, EF 303, EF 352 (manufactured by Jamco), MEGAFACE F171, F173, R-30 (manufactured by Dainippon Ink Chemicals Co., Ltd.), FLORARD FC430, FC431 (Sumitomo 3M Chemicals) Industrial (stock) manufacturing), ASAHIGUARD AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.).

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 layer coating liquid formed in the image forming layer.

[Related polymer blends]

The layer film coating liquid formed as described above may be mixed with other polymers (for example, highly insulating polymers) which can form a film in addition to the above-mentioned polyimide precursor or polyimine, and become a so-called polymer. The form of the blend.

In the polymer blend, by appropriately adjusting the structure of the polymer (the polyimine precursor, the polyimine, and other polymers described above), it is possible to form an underlayer film for forming an image. The concentration gradient of the polymer in the thickness direction of the film can be utilized as a useful means.

For example, in order to cause a change in the hydrophobicity of the film mainly on the surface of the film, as far as this is concerned, as long as the above-mentioned layer (surface layer) of the underlayer film for forming an image is present, the aforementioned polyamido having a thiol bond in the side chain exists. The amine precursor and/or polyimine can be used.

Therefore, when the film formation liquid under the formation of the image forming film is in the form of a polymer blend (hereinafter, the coating liquid of the form is referred to as a blend coating liquid), the polyimine precursor or the poly The blending ratio of the quinone imine is 1% by mass to 100% by mass in the solid content of the blend coating liquid. When it is 1% by mass or less, it is difficult to completely cover the outermost surface of the film when the blend coating liquid is formed on the film, and the ability to form an image is deteriorated.

The polymer blend is useful, for example, in the case of using a gate coating liquid for forming an image under the use of a gate insulating film which requires particularly 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, can be formed into a film by coating, and is solvent resistant to an organic semiconductor coating liquid (xylene, top three Various properties such as a polar solvent such as benzene and a low water absorption rate, but the performance required for insulation is particularly high. In order to achieve such high insulation properties, the imidization ratio of the film coating liquid formed under the above-mentioned image formation is at least 80% or more, and may be required to be 90% or more depending on the case, but conversely, the imidization ratio exceeds 90%. Solubility is lost when it is above %. In this case, by providing only a layer having a high insulating property in the lowermost layer of the insulating film, the layer formed by the layer coating liquid under the image formation described above is in the upper layer, and the insulating property of the insulating film can be maintained. It also eliminates solubility problems.

As described above, in order to form the lower layer of the lower layer film for forming an image as a high insulating layer, and the upper layer is a hydrophilic/hydrophobic conversion layer, the layers may be laminated in this order, but the operation is rather complicated.

At this time, the material of the high insulating layer is mixed with the material of the hydrophilic-hydrophobic conversion layer (that is, the aforementioned polyimide precursor and/or polyimine), and at this time, if the polarity or molecular weight of the upper material is lower than the lower layer If the mixture is coated on a substrate and dried to evaporate the solvent, the above-mentioned concentration gradient (herein referred to as layer separation) can be easily controlled by the action of forming the layer by moving the upper layer material to the surface. .

The material for forming the high insulating film of the lower layer described above is preferably a soluble polyimine. When the soluble polyimine is used as the underlayer material, the imidization ratio of the polyimine in the solution is preferably from the viewpoint of the insulating property, and is preferably at least 50% or more, preferably 80% or more. , preferably 90% or more.

Other materials which can be used as the underlayer material are exemplified by general organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinyl phenol, polyisobutylene, polymethyl methacrylate and the like.

The preferred soluble polyimine is exemplified by a soluble polyimine consisting of one or a plurality of structures selected from the group consisting of the structures of formula (16).

(In the formula, A represents an aliphatic ring or a tetravalent organic group composed only of an aliphatic group, and D represents a divalent organic group).

The molecular weight of the above-mentioned soluble polyimine is preferably from 2,000 to 200,000, more preferably from 5,000 to 50,000, by weight average molecular weight (result as measured by GPC) in terms of polyethylene glycol (or polyethylene oxide).

In the formula (16), specific examples of A are exemplified by a tetravalent organic group selected from A-1 to A-25, and specific examples of D are exemplified as D-1 to D-57. Among them, from the viewpoint of making the soluble polyimine having high solubility, it is preferable that the structure of A is A-5, A-6, A-16, A-18, A-19, A-20, A- 21, A-22, A-25 four-valent organic group, D is constructed as D-7, D-8, D-9, D-12, D-19, D-20, D-22, D-29 , a divalent organic group of D-39, D-41, and D-42.

These soluble polyimines may be used singly or in combination of plural kinds.

Further, when the polymer blend is used, for example, in an organic transistor having a film thickness of about 400 nm, the polyimine precursor and/or polyimine which are necessary for providing an upper layer (hydrophobic cross-linking layer) is used. The content ratio in the polymer blend may be 1% by mass or more. When there is too little, there is a case where there is a large variation in the surface properties of the underlying film for the image. It is preferably 5% by mass or more.

[Method for Producing Underlayer Film for Coating Film and Forming Image]

Applying the above-mentioned image forming film under the image forming method to polypropylene, poly by a dipping method, a spin coating method, a transfer printing method, a roll coating method, an inkjet method, a spray coating method, a brush coating method, or the like. On the plastic substrate or glass substrate, etc., which are widely used, such as ethylene, polycarbonate, polyethylene terephthalate, polyether oxime, polyethylene naphthalate, polyimine, etc., followed by a hot plate or An oven or the like is pre-dried to form a coating film. Then, the coating film is subjected to a heat treatment to form an underlayer film for forming an image which can be used as an underlayer film or an insulating film for forming an image.

The heat treatment method is not particularly limited, and can be exemplified by a method using a hot plate or an oven in an atmosphere of an appropriate atmosphere, that is, an inert gas such as air or nitrogen, or a vacuum.

The firing temperature is preferably from 180 ° C to 250 ° C from the viewpoint of promoting the thermal imine of the polyimide precursor, and is preferably 180 ° C or less from the viewpoint of film formation on a plastic substrate.

It is also possible to use a temperature change of two or more stages for firing. The staged firing can further improve the uniformity of the resulting film.

When the underlayer film for forming an image is formed, the film coating liquid under the image formation can be directly used for coating the substrate because it is in the form of a polyimide precursor and/or a polyimide and the solvent. In order to adjust the concentration, or to ensure the flatness of the coating film, or to improve the wettability of the coating liquid to the substrate, the surface tension of the coating liquid, the polarity, and the boiling point, etc., the above solvent may be added, and various other various substances may be added. The solvent is used as a coating liquid.

Specific examples of such solvents include, in addition to the solvent described in the first paragraph of the above-mentioned specification, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl card. Alcohol acetate, ethylene glycol, etc., 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, Propylene glycol derivatives such as 2-(2-methoxypropoxy)propanol, 2-(2-ethoxypropoxy)propanol and 2-(2-butoxypropoxy)propanol, lactic acid A lactic acid derivative such as methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate. These can be used alone or in combination.

Further, from the viewpoint of improving the preservability of the coating liquid and the uniformity of the film thickness of the coating film, it is preferred that 20 to 80% by mass of the total amount of the solvent is selected from N,N-dimethylformamide, N,N- At least one solvent of dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl hydrazine.

The concentration of the coating liquid is not particularly limited, but the solid concentration of the polyimine precursor and the polyimine is preferably from 0.1 to 30% by mass, more preferably from 1 to 10% by mass. These can be arbitrarily set by the specification of the coating apparatus or the obtained film thickness.

When the underlayer film for forming an image of the present invention produced as described above is used as a lower layer film for forming an image, if the film thickness is too thin, the patterning property after ultraviolet irradiation is lowered, and if it is too thick, the surface uniformity is impaired. Accordingly, the film thickness thereof is preferably from 5 nm to 1000 nm, more preferably from 10 nm to 300 nm, still more preferably from 20 nm to 100 nm.

Further, the underlayer film for forming an image of the present invention can also function as an insulating film when the insulating property is sufficiently high. In this case, the underlayer film for forming an image is used as a gate insulating film directly on the gate electrode, for example, in an organic FET device. In this case, in order to secure the insulating property, the film thickness of the underlayer film for forming an image is preferably thicker than when it is used as the underlayer film for forming the image. The film thickness thereof is preferably from 20 nm to 1000 nm, more preferably from 50 nm to 800 nm, most preferably from 100 nm to 500 nm.

[Method of Manufacturing Electrode for Forming Image]

The underlayer film for forming an image of the present invention is irradiated with ultraviolet rays in a pattern, and then an image forming electrode is produced by applying an image forming liquid described later.

In the present invention, the method of irradiating the lower layer film for forming an image into a pattern is not particularly limited, and for example, a method of irradiating with a mask in which an electrode pattern is drawn, and a method of drawing an electrode pattern using laser light is exemplified. Wait.

The material or shape of the mask is not particularly limited as long as the region necessary for the electrode is transmitted through the ultraviolet ray, and the region other than the ultraviolet ray is not transmitted.

In this case, the wavelength of the ultraviolet light to be used is usually in the range of 200 nm to 500 nm, and it is preferred to select a suitable ultraviolet wavelength which is suitable for the type of the underlayer film for forming an image to be used. Specifically, wavelengths of 248 nm, 254 nm, 303 nm, 313 nm, and 365 nm are exemplified. It is preferably 248 nm or 254 nm.

In the formation image of the present invention, the surface energy of the underlayer film is gradually increased by ultraviolet irradiation, and the irradiation amount is sufficiently saturated. The increase in the 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.

According to this, when the image forming liquid is applied onto the underlayer film for forming an image of the present invention after ultraviolet irradiation, the image forming liquid forms a self-organization along the pattern shape drawn by the surface energy difference on the underlying film for forming the image. With the pattern, an electrode of any shape can be obtained.

In this case, it is necessary to irradiate the amount of ultraviolet rays to form the lower layer film for image formation so that the contact angle of the image forming liquid is sufficiently changed. However, in terms of energy efficiency and time for shortening the production step, it is preferably 20 J/cm ^{2 .} Hereinafter, it is more preferably 10 J/cm ² or less, and most preferably 5 J/cm ² or less.

Further, the larger the difference in the contact angle between the ultraviolet ray irradiation portion forming the lower layer film for the image and the image forming liquid in the non-irradiation portion, the easier the pattern is formed, and the electrode can be processed into a complicated pattern or a fine pattern. Therefore, the amount of change in the contact angle by ultraviolet irradiation is preferably 5 or more, more preferably 10 or more, and most preferably 20 or more.

For the same reason, the contact angle of the preferred image forming liquid is 30° or more in the ultraviolet non-irradiated portion and 20° or less in the ultraviolet irradiation portion.

At present, since water is often used as the solvent for the image forming liquid, the performance evaluation of the underlayer film can be easily evaluated by changing the amount of change in the contact angle of the image forming liquid in accordance with the amount of change in the contact angle of water.

The image forming liquid in the present invention is a coating liquid which can be used as a functional film by evaporating the solvent contained therein after being applied onto a substrate, and is, for example, dissolved or uniformly dispersed in a charge transporting substance. It is made up of at least one solvent. Here, the charge transport property is synonymous with conductivity, and means any one of hole transportability, electron transport property, and hole and electron charge transportability.

The charge transporting substance is not particularly limited as long as it has conductivity capable of transporting holes or electrons. Examples thereof are metal fine particles such as gold, silver, copper, aluminum, or inorganic materials such as carbon black, fullerenes, and carbon nanotubes, or polythiophenes, polyanilines, polypyrroles, polyfluorenes, and derivatives thereof. Such as organic π conjugated polymers and the like.

Further, in order to increase the charge transporting ability of the charge transporting substance, a halogen, a Lewis acid, a protic acid, or a transition metal compound may be further added to the image forming liquid (specific examples are Br ₂ , I ₂ , Cl ₂ , FeCl ₃ , MoCl). ₅ , charge accepting substances such as BF ₃ , AsF ₅ , SO ₃ , HNO ₃ , H ₂ SO ₄ , polystyrene sulfonate, etc., or alkali metal or alkylammonium ions (specific examples are Li, Na, K) A charge supply substance such as Cs, tetraethylammonium or tetrabutylammonium or the like is used as a dopant.

The solvent of the image forming liquid is not limited as long as it can dissolve or uniformly disperse the above-mentioned charge transporting substance or dopant. However, from the viewpoint of obtaining a correct electrode pattern, it is preferred to exhibit a sufficiently large contact angle with respect to the ultraviolet non-irradiated portion forming the underlayer film for image formation, and it is less harmful to the underlayer film for forming an image of the present invention. In other words, it is preferably water or various alcohols.

Further, N,N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidine Polar solvents such as ketone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethyl hydrazine, and tetramethyl urea are also excellent in solubility in organic charge transporting substances. It is preferable from the viewpoint that the ultraviolet non-irradiated portion of the underlayer film is formed to have a sufficiently large contact angle, but these are preferably used in a range in which the damage of the underlayer film for forming an image of the present invention is minimized.

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.

Specific examples of the image forming liquid of the present invention include Baytron (registered trademark) P (polyethylidene dioxythiophene, manufactured by Bayer Co., Ltd.).

In the electrode of the present invention, the image forming liquid is applied onto the underlayer film for forming an image of the present invention to form a pattern, and then a solvent is evaporated to produce the film. The evaporation method of the solvent is not particularly limited, but it can be evaporated by using a hot plate or an oven in an appropriate atmosphere, that is, an inert gas such as air or nitrogen, or a vacuum to obtain a uniform film formation surface.

The temperature of the solvent to be evaporated is not particularly limited, and it is preferably carried out at 40 to 250 °C. From the viewpoint of maintaining the shape of the pattern and uniformity of the film thickness, it is also possible to use a temperature change of two or more stages.

The electrode formed of the image forming liquid can be used not only as a wiring for connecting electronic devices but also as an electrode for an electric device such as an electric field effect transistor, a bipolar transistor, various diodes, or various inductors.

The electronic device of the present invention is the electrode having the above-described present invention.

The following is an example in which the underlayer film for forming an image of the present invention is used in an organic FET device, but the present invention is not limited to these.

First, a highly doped n-type germanium substrate is prepared. Preferably, the substrate is preliminarily cleaned by washing with a lotion, alcohol, pure water or the like, and subjected to surface treatment such as ozone treatment or oxygen-plasma treatment before use. SiO ₂ , Ta ₂ O ₅ , Al ₂ O ₃ or the like is formed on the substrate by thermal oxidation, sputtering, CVD, vapor deposition or the like to form a gate insulating film. The film thickness of the gate insulating film varies depending on the application of the organic FET, but it is preferably in the range of 30 nm to 1000 nm in terms of driving voltage and electrical insulating properties.

Next, a layer containing a polyimine precursor having a repeating structure represented by the above formula (1) and/or a polyimine is formed on the insulating film in the above-described order. The film thickness of the layer is preferably from 20 nm to 100 nm. Subsequently, ultraviolet rays are irradiated using a mask or the like for obtaining a desired electrode shape.

Next, an image forming liquid using a polar solvent such as water is applied onto the surface of the underlayer film for forming an image. The applied image forming liquid repels the hydrophobic portion (ultraviolet-irradiated portion) and accelerates to the hydrophilic portion (ultraviolet irradiation portion) to be stabilized and dried to form a patterned source and a drain electrode. The coating method of the image forming liquid is not particularly limited to a spin coating method or a casting method, but is preferably an ink jet printing method or a spray coating method which is easy to control the amount of liquid.

Finally, the organic semiconductor material such as pentacene or polyolefin of the active layer of the organic FET is formed into a film. The film formation method of the organic semiconductor material is not particularly limited, and examples thereof include vacuum evaporation, a solution spin coating method, a casting method, an inkjet printing method, and a spray coating method.

In this way, the fabricated organic FET can greatly reduce the number of manufacturing steps, and an organic FET having a shorter channel than the mask vapor deposition method can be fabricated. Therefore, when a low mobility organic semiconductor material is used as the active layer, a large current may be taken out. . Further, since the underlayer film for forming an image obtained by the method of the present invention also has excellent electrical insulating properties, it can also be used as a gate insulating layer, and the manufacturing steps can be simplified.

[Examples]

The invention is illustrated in more detail below by way of examples, but the invention is not limited thereto.

[Determination of number average molecular weight and weight average molecular weight]

The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) of the polyimide precursor obtained by the following synthesis examples are GPC (normal temperature gel permeation chromatography), and the following apparatus and measurement were carried out. The conditions were measured and calculated based on the value of 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 Denko (share) (KD803, KD805 series)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide

(As an additive: lithium bromide-hydrate (LiBr‧H ₂ O) 30 mmol/L, phosphoric acid ‧ anhydrous crystals (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10 ml/L)

Flow rate: 1.0ml/min

Standard sample for calibration line preparation:

TSK standard polyethylene oxide manufactured by TOSOH (molecular weight: about 900,000, 150,000, 100,000, 30,000)

Polyethylene glycol manufactured by Polymer ‧ Laboratory (molecular weight: about 12,000, 4,000, 1,000)

[Measurement of film thickness]

The film thickness of the polyimide film is a part of the peeling film of the dicing blade, and a fully automatic fine shape measuring machine (ET4000A, manufactured by Otaru Research Institute Co., Ltd.) is used, and the measuring force is 10 μN, and the scanning speed is 0.05 mm/ Determined by measuring the step difference in seconds.

[UV irradiation]

The ultraviolet ray was irradiated onto the polyimide film by a band pass filter using light having a wavelength of 254 nm using a high pressure mercury lamp as a light source.

Further, the amount of exposure on the polyimide film was measured by an illuminometer (manufactured by OAI Co., Ltd., MODEL 306), and was attached to a Deep UV probe having a high peak sensitivity at a wavelength of 253.7 nm to measure the illuminance of the ultraviolet ray.

The obtained illuminance is 45 to 50 mW/cm ² . The obtained illuminance was multiplied by the exposure time as the exposure amount (J/cm ² ).

[Measurement of contact angle]

The contact angle was measured in a constant temperature and humidity environment (25 ° C ± 2 ° C, 50% RH ± 5%) using a fully automatic contact angle meter CA-W (manufactured by Kyowa Interface Chemical Co., Ltd.).

The contact angle of water was measured by the amount of liquid 3 μL, and after standing for 5 seconds after liquid administration.

The contact angle of propylene glycol monomethyl ether (PGME) was measured by a liquid amount of 3.0 to 3.5 μL, and after standing for 5 seconds after liquid administration.

<Synthesis Example> [Synthesis Example 1: Synthesis of Diamine Compound (DA-1: Octadecyl 3,5-Diaminothiobenzoate)]

A solution of the compound [ii] (20.00 g, 69.79 mmol) and triethylamine (8.07 g, 79.76 mmol) in tetrahydrofuran (155 g) was cooled to 10 ° C under nitrogen atmosphere, and the compound was added dropwise while paying attention to heat. i] (15.33 g, 66.47 mmol) in tetrahydrofuran (70 g). After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC (high-speed liquid chromatography), the reaction liquid was drained and poured into distilled water (1.8 L), and the precipitated solid was filtered, washed with water, and then washed with methanol (192 g) to obtain compound [iii] ( Yield: 26.4 g, yield: 83%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 9.21-9.20 (1H, m), 9.07-9.06 (2H, m), 3.18 (12H, t), 1.73-1.67 (2H, m), 1.48-1.37 (2H, m), 1.23 (28H, s), 0.86 (3H, t).

A mixture of the compound [iii] (19.95 g, 41.5 mmol), iron powder (reduced iron, 13.91 g, 249.0 mmol) and ethyl acetate (180 g) was heated to 70 ° C under a nitrogen atmosphere, and then ammonium chloride was added dropwise. (6.66 g, 124.5 mmol) of a 10% aqueous solution. After confirming the completion of the reaction by HPLC, the solid was filtered through Celite. After washing with 200 mL of each of ethyl acetate and distilled water, the aqueous layer was removed, and the organic layer was washed three times with distilled water (300 mL). Subsequently, the organic layer was dried over anhydrous magnesium sulfate, filtered, and then evaporated. The crude product of the obtained compound (DA-1) was recrystallized from methanol (104 g) to give Compound (DA-1) (yield: 11.7 g, yield: 67%).

^{1 H-NMR (400MHz, CDCl} 3, δppm): 6.69 (2H, dd), 6.18 (1H, t), 3.69 (4H, brs), 3.00 (2H, t), 1.66-1.56 (2H, m), 1.42-1.25 (30H, m), 0.88 (3H, t).

[Synthesis Example 2: Synthesis of Polyimine Precursor (PI-1)]

Under a nitrogen flow, 1.2621 g (0.003 mol) of 3,5-diaminooxybenzoic acid octadecyl ester (DA-1) prepared in Synthesis Example 1 was placed in a 50 mL four-necked flask, and dissolved in 10.42 g. After N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 0.5766 g (0.003 mol) of 1,2,3,4-cyclobutanetetracarboxylic anhydride (hereinafter referred to as CBDA) was added thereto. The polymerization reaction was carried out by stirring at 23 ° C for 10 hours, and further diluted with NMP to obtain an 8 mass% solution of the polyimine precursor (PI-1).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-1) were Mn = 11,650 and Mw = 28,380, respectively.

[Synthesis Example 3: Synthesis of Polyimine Precursor (PI-2)]

Under a nitrogen flow, DA-10.8835g (0.0021mol) and p-phenylenediamine (p-PDA) 0.0973g (0.0009mol) were placed in a 50mL four-necked flask, dissolved in 8.83g of NMP, and 0.5766g was added. (0.00294 mmol) of CBDA was stirred at 23 ° C for 10 hours to carry out a polymerization reaction, and then diluted with NMP to obtain a 6 mass% solution of a polyimine precursor (PI-2).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-2) were Mn = 34,670 and Mw = 97,560, respectively.

[Synthesis Example 4: Synthesis of Polyimine Precursor (PI-3)]

Under a nitrogen flow, 15.065 g (0.040 mol) of 1-octadecyloxy-2,4-diaminobenzene (APC18) was placed in a 200 mL four-necked flask, and dissolved in 127.6 g of NMP, and 7.45 was added. g (0.038 mol) of CBDA was stirred at 23 ° C for 12 hours to carry out polymerization, and then diluted with NMP to obtain a 6 wt% solution of polyimine precursor (PI-3).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-3) were Mn = 16,000 and Mw = 48,000, respectively.

[Synthesis Example 5: Diamine Compound (DA-2)]

Synthesis of DA-2

The compound [iv] (42.63 g, 209.9 mmok), compound [v] (102.97 g, 230.9 mmok), copper powder (29.35 g, 461.8 mmok), 2, 2'-linked were stirred at 120 ° C under a nitrogen atmosphere. A mixture of pyridine (3.28 g, 20.99 mmol) and dimethyl hydrazine (341 g). After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (2730 g), filtered, and the filtrate was washed with distilled water (2 L) and ethyl acetate (1.5 L). Next, hexane (500 g) was added to the filtrate, and the organic layer was washed three times with saturated brine (1 L) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered and evaporated to give Compound [vi] (yield: 75.33 g, yield: 81%). ¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.48 (2H, d), 7.32 (2H, d), 2.52 (3H, s).

N-Fluoro-N'-(chloromethyl)triethylenediamine bis (N-fluoro-N'-(chloromethyl)triethylenediamine bis(N) was added to a solution of compound [vi] (52.00 g, 117.6 mmol) in acetonitrile (347 g) / purified water (17 g). Tetrafluoroborate) (43.63 g, 123.2 mmol) was reacted at 23 °C. After confirming the completion of the reaction by HPLC, the solvent was distilled off. Next, dichloromethane (1.2 L) was added, and a saturated aqueous sodium hydrogencarbonate solution (700 mL) was added in small portions. After the aqueous layer was removed, the organic layer was washed three times with saturated brine (700 mL). Subsequently, the solvent was distilled off by filtration to obtain a compound [vii] (yield: 48.05 g, yield: 89%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.81 (2H, d), 7.78 (2H, d), 2.71 (3H, s).

Acetic anhydride (46.39 g, 454.4 mmol) was added to the compound [vii] (26.03 g, 56.8 mmol) under a nitrogen atmosphere, and the reaction was carried out under reflux with heating. After confirming the completion of the reaction by HPLC, the solvent was distilled off to obtain a crude product of compound [viii]. The obtained crude product was purified by column chromatography (SiO ₂ , hexane / ethyl acetate) to yield compound [viii] (yield: 24.11 g, yield: 85%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.54 (4H, s), 5.50 (2H, s), 2.14 (3H, s).

Under a nitrogen atmosphere, a 28% aqueous ammonia solution (13.73 g) was added to a solution of the compound [viii] (37.67 g, 75.3 mmol) in methanol (150 g), and stirred at 23 °C. After confirming the completion of the reaction by HPLC, the pH was adjusted to 6 with 35% hydrochloric acid, and then the solvent was evaporated. Subsequently, the crude product was dissolved in dichloromethane (1 L), washed three times with saturated brine (500 mL) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered and evaporated to give Compound [ ix] (yield: 31.28 g, yield: 97%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.44 (2H, d), 7.37 (2H, d), 3.61 (1H, s).

The solution containing the compound [ix] (31.00 g, 72.4 mmol) and triethylamine (7.33 g, 72.4 mmol) in tetrahydrofuran (139 g) was cooled to below 10 ° C under nitrogen atmosphere, and the compound was added dropwise while paying attention to heat. [i] (15.90 g, 68.95 mmol) in tetrahydrofuran (100 g). After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (1.9 L), and the precipitated solid was filtered, washed with water and then recrystallized from 2-propanol (257 g) to give compound [x] (yield: 27.01 g, yield. Rate: 63%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 9.30 (1H, t), 9.15 (2H, d), 7.74 (4H, q).

The compound [x] (14.00 g, 22.5 mmol), 3% platinum-carbon (supporting 0.3% iron, water, 2.8 g, 20 wt%), methanol (hydrogen) was stirred at 23 ° C in the presence of hydrogen under a nitrogen atmosphere. A mixture of 210 g). After confirming the completion of the reaction by HPLC, the reaction mixture was filtered over celite, and the celite was washed with methanol (50 mL), and the solvent was distilled off. The crude product of the obtained compound (DA-2) was washed with 2-propanol (60 g), and filtered and dried to give Compound (DA-2) (yield: 9.13 g, yield: 72%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.65 (4H, s), 6.73 (2H, d), 6.24 (1H, t), 3.76 (4H, brs).

[Synthesis Example 6: Diamine Compound (DA-3)]

Synthesis of DA-3

The compound [iv] (27.05 g, 133.2 mmol), the compound [xi] (80.00 g, 146.5 mmol), copper powder (18.62 g, 293.0 mmol), 2, 2'-linked were stirred at 120 ° C under a nitrogen atmosphere. A mixture of pyridine (2.08 g, 13.32 mmol) and dimethyl hydrazine (216 g). After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (1730 g), filtered, and the filtrate was washed with distilled water (1 L) and ethyl acetate (1 L). Next, hexane (500 g) was added to the filtrate, and the organic layer was washed three times with saturated brine (1 L) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered off, and the compound [xii] (yield: 65.72 g, yield: 91%) was obtained.

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.58 (2H, d), 7.47 (2H, d), 2.54 (3H, s).

N-Fluoro-N'-(chloromethyl)triethylenediamine bis (by a solution of the compound [xii] (50.00 g, 92.21 mmol) in acetonitrile (333 g) / purified water (17 g) Tetrafluoroborate) (32.67 g, 92.21 mmol) was reacted at 23 °C. After confirming the completion of the reaction by HPLC, the solvent was distilled off. Next, dichloromethane (800 mL) was added, and a saturated aqueous sodium hydrogencarbonate solution (500 mL) was added in small portions. After the aqueous layer was removed, the organic layer was washed three times with brine (500 mL) Subsequently, solvent distillation was carried out by filtration to obtain a compound [xiii] (yield: 47.98 g, yield: 93%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.81 (2H, d), 7.77 (2H, d), 2.78 (3H, s).

Trifluoroacetic anhydride (220.56 g, 1.05 mol) was added to the compound [xiii] (70.63 g, 126.5 mmol) under a nitrogen atmosphere, and the reaction was carried out under reflux with heating. After confirming the completion of the reaction by HPLC, the solvent was evaporated to give a crude product. Next, methanol (226 g) and triethylamine (211.89 g) were added, and the mixture was stirred at 23 ° C for 30 minutes, and then the solvent was distilled off. Next, the obtained crude product was dissolved in ethyl acetate (1 L), and the mixture was washed twice with saturated aqueous ammonium chloride (1 L) and brine (1L). Compound [xiv] (yield: 64.7 g, yield: 97%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.44 (2H, d), 7.36 (2H, d), 3.61 (1H, s).

The solution containing the compound [xiv] (69.00 g, 130.62 mmol) and triethylamine (13.22 g, 130.62 mmol) in tetrahydrofuran (290 g) was cooled to below 10 ° C under nitrogen atmosphere, and the compound was added dropwise while taking care of the heat. i] (28.68 g, 124.40 mmol) in tetrahydrofuran (145 g). After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (3.5 L), and the precipitated solid was filtered, washed with water and then recrystallized from 2-propanol (270 g) to obtain compound [xv] (yield: 77.99 g, Yield: 88%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 9.27 (1H, t), 9.17 (2H, d), 7.61 (4H, q).

The compound [xvii] (8.00 g, 11.1 mmol), 3% platinum-carbon (supporting 0.3% iron, water, 1.6 g, 20 wt%), methanol (supported under stirring in a hydrogen atmosphere at 23 ° C in a nitrogen atmosphere) a mixture of 120 g). After confirming the completion of the reaction by HPLC, the reaction mixture was filtered over celite, and the celite was washed with methanol (30 mL), and the solvent was distilled off. The crude product of the obtained compound (DA-3) was washed with 2-propanol (28 g), and filtered and dried to give Compound (DA-3) (yield: 5.6 g, yield: 76%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.65 (4H, s), 6.73 (2H, d), 6.24 (1H, t), 3.76 (4H, brs).

[Synthesis Example 7: Diamine Compound (DA-4)]

Synthesis of DA-4

The solution containing the compound [xvi] (21.87 g, 45.54 mmol) and triethylamine (4.61 g, 45.54 mmol) in tetrahydrofuran (90 g) was cooled to below 10 ° C under nitrogen atmosphere, and the compound was added dropwise while paying attention to heat. i] (10.00 g, 43.37 mmol) in tetrahydrofuran (60 g). After the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC (High Speed Liquid Chromatography), the reaction mixture was poured into distilled water (1.2 L), and the precipitated solid was filtered, washed with water, and washed with 2-propanol (232 g) to obtain a compound [ Xvii] (yield: 27.69 g, yield: 95%).

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 9.06 (1H, t), 8.86 (2H, d), 3.44 (2H, t), 2.79-2.66 (2H, m).

The mixture containing the compound [xvii] (25.00 g, 37.1 mmol), iron powder (reduced iron, 12.42 g, 222.5 mmol) and ethyl acetate (225 g) was heated to 70 ° C under a nitrogen atmosphere, and chlorination was added dropwise. A 10% aqueous solution of ammonium (5.95 g, 111.3 mmol). After confirming the completion of the reaction by HPLC, the solid was filtered with celite. After washing with 500 mL of each of ethyl acetate and distilled water, the aqueous layer was removed, and the organic layer was washed three times with distilled water (500 mL). Subsequently, the organic layer was dried over anhydrous magnesium sulfate, and filtered, and then evaporated. The crude product of the obtained compound (DA-4) was washed with hexane (60 g), filtered, and dried to give Compound (DA-4) (yield: 19.5 g, yield: 85%).

^{1 H-NMR (400MHz, DMSO} -d 6, δppm): 6.36 (2H, d), 6.06 (1H, t), 5.14 (4H, brs), 3.19 (2H, t), 2.64-2.51 (2H, m ).

[Synthesis Example 8: Synthesis of Polyimine (PI-4)]

In a nitrogen gas stream, 3.5837 g (8.73 mmol) of 2,2-bis(4-aminophenoxyphenyl)propane (hereinafter referred to as BAPP) and 0.1518 g (0.27 mmol) were injected into a 100 mL four-necked flask. After DA-2, and dissolved in 36.02g of NMP, add 2.6214g (8.73mmol) of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (hereinafter referred to as It was TDA), and it was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The resulting solution of polyamic acid was diluted to 8 mass% with NMP.

To 30 g of this solution, 11 g of acetic anhydride as a ruthenium iodide catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized by ¹ H-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of γ-butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-4).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine (PI-4) were Mn = 14,300 and Mw = 38,000, respectively.

[Synthesis Example 9: Synthesis of Polyimine (PI-5)]

3.4728 g (8.46 mmol) of BAPP and 0.3037 g (0.54 mmol) of DA-2 were placed in a 100 mL four-necked flask under a nitrogen stream, and after dissolving in 36.25 g of NMP, 2.6214 g (8.73 mmol) was added. TDA was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The resulting solution of polyamic acid was diluted to 8 mass% with NMP.

To 30 g of this solution, 11 g of acetic anhydride as a ruthenium-imiding catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be imidized by 90% or more by ¹ H-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of γ-butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-5).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine (PI-5) were Mn = 16,400 and Mw = 39.400, respectively.

[Synthesis Example 10: Synthesis of Polyimine (PI-6)]

3.6206 g (8.82 mmol) of BAPP and 0.1192 g (0.18 mmol) of DA-3 were placed in a 100 mL four-necked flask under a nitrogen stream, and after dissolving in 36.05 g of NMP, 2.6214 g (8.73 mmol) was added. The TDA was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The resulting solution of polyamic acid was diluted to 8 mass% with NMP.

To 30 g of this solution, 11 g of acetic anhydride as a ruthenium-imiding catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be imidized by 90% or more by ¹ H-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of γ-butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-6).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine (PI-6) were Mn = 20,200 and Mw = 51,400, respectively.

[Synthesis Example 11: Synthesis of Polyimine (PI-7)]

3.9819 g (9.7 mmol) of BAPP and 0.1842 g (0.3 mmol) of DA-4 were placed in a 100 mL four-necked flask under a nitrogen stream, and after dissolving in 40.11 g of NMP, 2.9126 g (9.7 mmol) was added. The TDA was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The resulting solution of polyamic acid was diluted to 8 mass% with NMP.

To 30 g of this solution, 11 g of acetic anhydride as a ruthenium iodide catalyst and 5.2 g of pyridine were added, and reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized by ¹ H-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of γ-butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-7).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine (PI-7) were Mn = 17,800 and Mw = 45,000, respectively.

[Synthesis Example 12: Synthesis of Polyimine Precursor (PI-8)]

3.9819 g (9.7 mmol) of BAPP and 0.1842 g (0.3 mmol) of DA-4 were placed in a 100 mL four-necked flask under a nitrogen stream, and after dissolving in 34.39 g of NMP, 1.9023 g (9.7 mmol) was added. The CBDA was stirred at 23 ° C for 10 hours to carry out a polymerization reaction, and then diluted with NMP to obtain a 6 mass% solution of a polyimine precursor (PI-8).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-8) were Mn = 14,300 and Mw = 32,100, respectively.

[Synthesis Example 13: Synthesis of Polyimine (PI-9) for Blend]

4.86 g (0.045 mol) of p-phenylenediamine and 1.74 g (0.005 mol) of 4-hexadecyloxy-1,3-diaminobenzene were placed in a 200 mL four-necked flask under a nitrogen stream. After dissolving in 122.5 g of NMP, 15.01 g (0.05 mol) of TDA was added, and the mixture was stirred at room temperature for 10 hours to carry out polymerization. The resulting solution of polyamic acid was diluted to 8 mass% with NMP.

To 50 g of this solution, 10.8 g of acetic anhydride as a ruthenium iodide catalyst and 5.0 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized 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 (PI-9).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimine (PI-9) were Mn = 18,000 and Mw = 54,000, respectively.

[Synthesis Example 14: Modulation of polymer blend (composition A)]

9 g of a 6 wt% solution of the polyimine (PI-9) prepared in Synthesis Example 13 and 1 g of a 6 wt% solution of the polyimine (PI-7) prepared in Synthesis Example 11 were mixed, and stirred at room temperature 6 In hours, composition A was obtained.

[Synthesis Example 15: Preparation of polymer blend (composition B)]

9 g of a 6 wt% solution of polyimine (PI-9) prepared in Synthesis Example 13 and 1 g of a 6 wt% solution of polyimine (PI-8) prepared in Synthesis Example 12 were mixed, and stirred at room temperature 6 In hours, composition B was obtained.

[Synthesis Example 16: Preparation of Polymer Blend (Composition C)]

8 g of a 6 wt% solution of the polyimine (PI-9) prepared in Synthesis Example 13 and 2 g of a 6 wt% solution of the polyimine (PI-8) prepared in Synthesis Example 12 were mixed, and stirred at room temperature 6 In hours, composition C was obtained.

The structural formula of the tetracarboxylic anhydride and the diamine compound synthesized or used in the examples is shown below.

[Tetracarboxylic anhydride used in this example]

[Diamine used in this example]

<Example 1> Water contact angle change

On the glass substrate with ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-1 prepared in Synthesis Example 2 was dropped using a syringe equipped with a 0.2 μm pore filter by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 210 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. The water contact angle θ (°) of the polyimide film was measured.

Two sheets of polyimide film were produced in the same order, and after irradiating ultraviolet rays with an irradiation amount of 20 J/cm ² or 40 J/cm ² , the water contact angle θ (°) of the film was measured.

The results are shown in Table A.

<Example 2> Water contact angle change

Three sheets of polyimide film were produced in the same manner as in Example 1 except that the solution of PI-2 prepared in Synthesis Example 3 was used, and the film was irradiated with ultraviolet rays, irradiated with ultraviolet rays of 20 J/cm ² or irradiated with ultraviolet rays of 40 J/. The film of cm ² was measured for the water contact angle θ (°) of each film.

The results are shown in Table A.

<Comparative Example 1> Change in water contact angle

Two sheets of polyimide film were produced in the same manner as in Example 1 except that the solution of PI-3 prepared in Synthesis Example 4 was used, and each of the films was an ultraviolet non-irradiated film or a film irradiated with ultraviolet rays of 40 J/cm ² , and each film was measured. The water contact angle θ (°).

The results are shown in Table A.

<Example 3> PGME contact angle change

Three polyimine films were produced in the same manner as in Example 1, and each was an ultraviolet non-irradiated film, a film irradiated with ultraviolet rays of ² J/cm ² or a film irradiated with ultraviolet rays of 6 J/cm ² , and the contact angle of PGME of each film was measured. θ(°).

The results are shown in Table B.

<Comparative Example 2> PGME contact angle change

Two sheets of polyimide film were produced in the same manner as in Example 1 except that the solution of PI-3 prepared in Synthesis Example 4 was used, and each of the films was an ultraviolet non-irradiated film or a film irradiated with ultraviolet rays of 6 J/cm ² , and each film was measured. The PGME contact angle θ (°).

The results are shown in Table B.

<Example 4> Change in contact angle of PGME

On a glass substrate with ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-4 prepared in Synthesis Example 8 was dropped using a syringe equipped with a 0.2 μm pore filter by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. The contact angle θ (°) of the PGME solution of the polyimide film was measured.

One piece of the polyimide film was produced in the same order, and after irradiating ultraviolet rays with an irradiation amount of 1 J/cm ² , the PGME contact angle θ (°) of the film was measured.

The results are shown in Table C.

<Example 5> PGME contact angle change

Two sheets of polyimide film were produced in the same manner as in Example 4 except that PI-5 prepared in Synthesis Example 9 was used, and each of the films was irradiated with an ultraviolet ray-free film and irradiated with ultraviolet rays of 1 J/cm ^{2 to} measure the PGME of each film. Contact angle θ (°).

The results are shown in Table C.

<Example 6> PGME contact angle change

Two sheets of polyimide film were produced in the same manner as in Example 4 except that PI-6 prepared in Synthesis Example 10 was used, and each of the films was irradiated with an ultraviolet ray-free film and irradiated with ultraviolet rays of 1 J/cm ^{2 to} measure the PGME of each film. Contact angle θ (°).

The results are shown in Table C.

<Example 7> PGME contact angle change

Two sheets of polyimide film were produced in the same manner as in Example 4 except that the composition A prepared in Synthesis Example 14 was used, and each of the films was irradiated with an ultraviolet ray-free film and irradiated with ultraviolet rays of 1 J/cm ^{2 to} measure the PGME of each film. Contact angle θ (°).

The results are shown in Table C.

<Example 8> PGME contact angle change

In the same procedure as in Example 6, except that the composition C prepared in Synthesis Example 16 was used, two polyimide films were prepared in the same manner as in Example 6, and each of the films was irradiated with ultraviolet rays of 1 J/cm ² , and the PGME of each film was measured. Contact angle θ (°).

The results are shown in Table C.

As shown in Table A, Table B, and Table C, the PGME contact angle after ultraviolet irradiation in the examples using the polyimine and the polyimine precursor prepared from the diamine having a thiol bond in the side chain Any situation has changed dramatically.

On the other hand, in Comparative Examples 1 and 2 in which the polyimine precursor (PI-3) produced by using a diamine having a thiol bond in a side chain was not used, the amount of change in contact angle of water or PGME was small.

The result is considered to be that if the polyimine precursor is a structure in which a side chain is a thiol ester group, a hydrophobic machine exists, that is, the thiol ester gene is irradiated by ultraviolet light to cause photodecomposition, and the hydrophobic portion of the side chain is obtained. The autonomous strand is cleaved and separated, thereby causing a large change in the hydrophilicity and hydrophobicity.

<Example 9> Electrode patterning evaluation

On a glass substrate with ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-4 prepared in Synthesis Example 8 was dropped using a syringe equipped with a 0.2 μm pore filter by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. The polyimide film was irradiated with ultraviolet rays of 1 J/cm ² through a mask (line width of 100 μm and a pitch of 100 μm and space) to hydrophilize one part of the polyimide. Subsequently, the silver fine particle dispersion was added dropwise to the ultraviolet irradiation portion, and 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. 1. The film composed of PI-4 can form a silver electrode which becomes a target line width.

<Example 10> Electrode patterning evaluation

A polyimide film was formed in the same manner as in Example 9 except that the composition A prepared in Synthesis Example 14 was used. The polyimide film was passed through a mask (line width 100 μm, line and space of 100 μm). One part of the polyimine was hydrophilized by irradiating ultraviolet rays at 1 J/cm ² . Subsequently, the silver fine particle dispersion was added dropwise to the ultraviolet irradiation portion, and 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. The film composed of the composition A can form a silver electrode which becomes a target line width.

<Comparative Example 3> Electrode patterning evaluation

A polyimide film was formed in the same manner as in Example 11 except that PI-3 prepared in Synthesis Example 4 was used, and the firing temperature was 210 ° C. The film was passed through the mask on the polyimide film (line width). 100 μm, a line of 100 μm pitch and space) was irradiated with ultraviolet rays of 1 J/cm ² . Subsequently, the silver fine particle dispersion was added in a small amount, but since the ultraviolet irradiation portion was not hydrophilized, the electrode could not be formed.

The results of Examples 9 to 10 and Comparative Example 3 are shown in Table D.

A film composed of PI-4 having a thiol ester bond and a composition A has a hydrophilicity which is sufficiently changed by an ultraviolet irradiation amount of 1 J/cm ² to form a silver electrode having a line width of 100 μm, and conversely, In the film composed of the composition D of the thiol ester bond, the hydrophilicity of the ultraviolet irradiation amount of 1 J/cm ² was not sufficiently changed, and the electrode could not be formed.

<Example 11> Insulation

On the glass substrate with ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-1 prepared in Synthesis Example 2 was dropped using a syringe equipped with a 0.2 μm pore filter by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 210 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 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 is peeled off to expose the ITO, and then the diameter is laminated on the polyimide film and the ITO by using a vacuum evaporation device. 1.0 mm aluminum electrode with a film thickness of 100 nm. The vacuum vapor deposition conditions at this time were set to room temperature, the degree of vacuum was 3 × 10 ^-3 Pa or less, and the aluminum vapor deposition rate was 0.3 nm / sec or less. By forming an electrode above and below the polyimide film, a sample for evaluation of current-voltage characteristics of the polyimide film was prepared.

The prepared sample was immediately subjected to a current-voltage characteristic in a nitrogen atmosphere. The measured voltage is set to rise from 0V every 2V to 90V. The polyimine film at this time had a specific dielectric constant of 3.37 and a leakage current density of 3 × 10 ^-10 A/cm ² . Further, the electric field insulation of the polyimide film at 2 MV/cm was not broken.

Figure 3 shows the results of measurement of current-voltage characteristics in a nitrogen atmosphere.

Next, the same sample as above was allowed to stand in the atmosphere (25 degrees, humidity 45%) for 15 hours, and then the current-voltage characteristics were measured. The measured voltage is set to rise from 0V every 2V to 90V. The sample leakage current density at this time was 1.8 × 10 ^-7 A/cm ² .

Figure 4 shows the results of measurement of current-voltage characteristics in the atmosphere.

<Example 12> Insulation

A sample for current-voltage characteristic evaluation was produced in the same manner as in Example 11 except that the firing temperature of the polyimide film was 230 °C. The polyimine film at this time had a specific dielectric constant of 3.14 and a leakage current density of 1.0 × 10 ^-10 A/cm ² . Further, the electric field insulation of the polyimide film at 2 MV/cm was not broken.

Next, the same sample as above was allowed to stand in the atmosphere (25 degrees, humidity 45%) for 15 hours, and then the current-voltage characteristics were measured. The measured voltage is set to rise from 0V every 2V to 90V. The sample leakage current density at this time was 1.8 × 10 ^-8 A/cm ² .

Fig. 3 shows the results of measurement of current-voltage characteristics in a nitrogen atmosphere, and Fig. 4 shows the results of measurement of current-voltage characteristics in the atmosphere.

<Example 13> Insulation

On a glass substrate with ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-4 prepared in Synthesis Example 8 was dropped using a syringe equipped with a 0.2 μm pore filter by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 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 is peeled off to expose the ITO, and then the diameter is laminated on the polyimide film and the ITO by using a vacuum evaporation device. 1.0 mm aluminum electrode with a film thickness of 100 nm. The vacuum vapor deposition conditions at this time were set to room temperature, the degree of vacuum was 3 × 10 ^-3 Pa or less, and the aluminum vapor deposition rate was 0.3 nm / sec or less. By forming an electrode above and below the polyimide film, a sample for evaluation of current-voltage characteristics of the polyimide film was prepared.

The prepared sample was allowed to stand in an environment of 23 ° C ± 3 ° C and a humidity of 45% ± 5% for 15 hours, and then the current-voltage characteristics were measured. The measurement voltage was set to rise from 0 V every 2 V to 100 V. The leakage current density of this sample at 1 MV/cm was 4.3 × 10 ^-11 A/cm ² . Further, the polyimide film was not damaged until 2 MV/cm of insulation.

Figure 5 shows the results of current-voltage characteristics measurement.

<Example 14> Insulation

A sample for current-voltage characteristic evaluation was produced in the same manner as in Example 13 except that the composition A prepared in Synthesis Example 14 was used.

The leakage current density of this sample at 1 MV/cm was 1.7 × 10 ^-10 A/cm ² . Further, the polyimide film was not damaged until 2 MV/cm of insulation.

Figure 5 shows the results of current-voltage characteristics measurement.

<Example 15> Insulation

A sample for current-voltage characteristic evaluation was produced in the same manner as in Example 13 except that the composition B prepared in Synthesis Example 15 was used and the baking temperature was 230 °C.

The leakage current density of this sample at 1 MV/cm was 1.2 × 10 ^-10 A/cm ² . Further, the polyimide film was not damaged until 2 MV/cm of insulation.

Figure 5 shows the results of current-voltage characteristics measurement.

<Example 16> Insulation

A sample for current-voltage characteristic evaluation was produced in the same manner as in Example 13 except that the composition C prepared in Synthesis Example 16 was used and the baking temperature was 230 °C.

The leakage current density of this sample at 1 MV/cm was 3.4 × 10 ^-10 A/cm ² . Further, the polyimide film was not damaged until 2 MV/cm of insulation.

Figure 5 shows the results of current-voltage characteristics measurement.

As shown in Fig. 3, the film composed of PI-1 was an excellent insulating film in a nitrogen atmosphere (Example 11 and Example 12).

As shown in Fig. 4, the film composed of PI-1 is susceptible to moisture, and the leakage current density in the atmosphere is more increased than in the nitrogen atmosphere, but it is still used as a lower film for forming an image. The level of the problem (Example 11 and Example 12).

Further, as shown in Fig. 5, the film composed of PI-4 and the compositions A to C was an excellent insulating film (Examples 13 to 16).

In other words, the underlayer film for forming an image forming method of the present invention has a layer film which is a sufficient insulating property for forming an underlayer film for image formation.

<Example 17: Crystal characteristics>

On a glass substrate (2.5 cm side length, thickness 0.7 mm) with a Cr electrode, a solution of PI-4 prepared in Synthesis Example 8 was dropped using a syringe equipped with a 0.2 μm pore filter, and spin-coated. Method coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 nm. On the polyimide film, a portion of the polyimine was hydrophilized by irradiating ultraviolet rays of ² J/cm ² through a photomask. Subsequently, a silver fine particle dispersion liquid was added dropwise to the ultraviolet irradiation portion, and fired at 180 ° C for 60 minutes to form a source ‧ 汲 electrode having a thickness of 50 nm.

On the silver electrode, pentacene (manufactured by Aldrich) was formed into a film of 70 nm by vacuum evaporation. The vapor deposition rate of pentacene was set to 0.05 nm/second.

The electrical characteristics of the organic thin film transistor obtained above were evaluated by measuring the change in the source current with respect to the gate voltage.

In detail, the source ‧thole voltage (V _D ) is set to -80V, the gate voltage (V _G ) varies from +20V to -80V in 2V steps, and the voltage is maintained for 1 second before the current is fully stabilized. The latter value is recorded as the measured value of the drain current, and this operation is repeated 5 times. Further, the measurement was carried out by using a semiconductor parameter analyzer HP4156C (manufactured by AGILENT Technologies Co., Ltd.) in a nitrogen atmosphere.

Generally, the drain current I _D in a saturated state can be expressed by the following equation. That is, the mobility μ of the organic semiconductor can be obtained by plotting the slope of the graph when the square root of the absolute value of the drain current I _D is the vertical axis and the gate voltage V _G is plotted on the horizontal axis.

I _D = WCμ(V _G -V _T ) ² /2L

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, V _T is the threshold voltage of the transistor, and μ is the mobility. The transistor W made in this example was W = 2 mm, L = 100 μm, and C = 6.4 nF/cm ² .

The mobility of pentacene is calculated to be 5 × 10 ^-2 cm ² /Vs on the basis of this formula. Further, the threshold voltage is from -18V to -20V, and the ratio of the ON state to the OFF state (ON/OFF ratio) is 10 ⁶ levels. Further, repeated measurements were carried out without any transfer characteristic shift to obtain stability characteristics (Fig. 6).

The film obtained from PI-4 is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor.

<Example 18: Crystal characteristics>

An organic transistor was produced in the same manner as in Example 17 except that the composition A prepared in Synthesis Example 14 was used. The transistor W made in this example was W = 2 mm, L = 100 μm, and C = 6.5 nF/cm ² .

The mobility of pentacene is calculated to be 5 × 10 ^-2 cm ² /Vs on the basis of this formula. Further, the threshold voltage is from -19V to -21V, and the ratio of the on state to the off state (on/off ratio) is 10 ⁶ . Further, repeated measurement was carried out, and no characteristic shift was observed to obtain stability characteristics (Fig. 7).

The film obtained from the composition A is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor.

<Example 19: Crystal characteristics>

An organic transistor was produced in the same manner as in Example 17 except that the amount of ultraviolet irradiation was set to 1 J/cm ² . The transistor W made in this example had W = 2 mm, L = 100 μm, and C = 6.4 nF/cm ² .

The mobility of pentacene is calculated to be 3 × 10 ^-2 cm ² /Vs on the basis of this formula. Further, the threshold voltage is from -16V to -20V, and the ratio of the on state to the off state (on/off ratio) is 10 ⁶ levels. Further, repeated measurements were carried out, and no characteristic shift was observed to obtain stability characteristics (Fig. 8).

The film obtained from the composition A is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor.

[Industry possible use]

According to the underlayer film for forming an image of the present invention, it is possible to shorten the necessary exposure time for changing the hydrophilicity and hydrophobicity, and it is expected to reduce the manufacturing cost when forming a patterned layer of a functional material such as an electrode.

Further, by irradiating the polarized light UV, an anisotropy can be imparted to the film obtained from the polyimine precursor and the polyimine. In other words, it is possible to use an alignment treatment film which is a functional material such as a liquid crystal or a semiconductor, and it is expected to shorten the manufacturing time as in the case of forming an underlayer film for an image.

Fig. 1 is a photomicrograph showing a silver electrode on PI-4 produced in Example 9 (silver electrode line width: 100 μm).

Fig. 2 is a photomicrograph showing a silver electrode on the composition A produced in Example 10 (silver electrode line width: 100 μm).

Fig. 3 is a graph showing current-voltage characteristics of a polyimide film obtained by firing a polyimide precursor (PI-1) in a nitrogen atmosphere (Example 11 and Example 12).

Fig. 4 is a graph showing current-voltage characteristics of a polyimide film obtained by firing a polyimide precursor (PI-1) in the atmosphere (Example 11 and Example 12).

Fig. 5 is a graph showing current-voltage characteristics of the polyimide film produced in Examples 13 to 16 in the atmosphere.

Fig. 6 is a view showing the transmission characteristics of an organic transistor in which an electrode obtained by irradiating a film of PI-4 was irradiated with ² J/cm ^{2 of} ultraviolet rays and processed (Example 17).

Fig. 7 is a view showing the transmission characteristics of an organic transistor in which an electrode obtained by irradiating a film of the composition A with ² J/cm ^{2 of} ultraviolet rays and processing the electrode (Example 18).

Fig. 8 is a view showing the transmission characteristics of an organic transistor in which an electrode obtained by irradiating a film of PI-4 was irradiated with 1 J/cm ^{2 of} ultraviolet rays and an electrode was processed (Example 19).

Claims (14)

An underlayer film for forming an image, characterized by comprising a polyimine precursor containing a repeating structure represented by the following formula (1) or a polyimine imine obtained by dehydrating and ring-closing the polyimine precursor: (wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2) or (3), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents a natural number) ; (X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CH ₂ COO - or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon number An alkyl group of 1 to 3, and t represents an integer of 0 to 3.). An underlayer film for forming an image, which comprises reacting a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) with a diamine component containing a diamine represented by the following formula (7) The obtained polyimine precursor, or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: Wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or formula (3): (wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or An alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3)]. The underlayer film for forming an image as in the first aspect of the patent application, wherein Z of the formula (2) or the formula (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which is substituted with a fluorine atom by any hydrogen atom. The underlayer film for forming an image as in the first aspect of the patent application, wherein A represents a tetravalent organic group having an aliphatic ring or only an aliphatic group. The underlayer film for forming an image as in the first aspect of the patent application, wherein B represents a divalent structure represented by the formula (2). An underlayer film for forming an image as in the first aspect of the patent application, wherein X and Y represent a single bond. An organic transistor characterized by comprising the underlayer film for forming an image according to any one of claims 1 to 6. a diamine compound represented by the following formula (14) or the following formula (15), (wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, and R each independently represents a fluorine atom and an alkyl group having 1 to 3 carbon atoms. An oxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. A polyimine which is characterized by containing a polyimine precursor having a repeating unit represented by the following formula (1) or dehydrating and ring-closing the polyimine precursor, (wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2a) or (3a), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and n represents a natural number) ; (wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-, -CONH-, -CH ₂ O-, - CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, and R each independently represents a fluorine atom and an alkyl group having 1 to 3 carbon atoms. An oxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. An image forming underlayer film coating liquid comprising a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine containing a diamine represented by the following formula (7) The polyimine precursor obtained by the reaction of the component, or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or formula (3): R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -O-, -COO-, -OCO-. , -CONH-, -CH ₂ O-, -CH ₂ COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R independently represents a fluorine atom, An alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. The underlayer film coating liquid is formed by the method of claim 10, wherein Z of the formula (2) or the formula (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms in which any hydrogen atom is substituted with a fluorine atom. The underlayer film coating liquid for forming an image according to claim 10, further comprising a soluble polyimine having a ruthenium iodide ratio of 80% or more. a film formed under the portrait, which is characterized by a patent application The formation of the underlayer film coating liquid in the form of the items 10 to 12 is obtained by firing. An organic transistor characterized by having a film obtained by firing an underlayer film coating liquid of the image forming method of Items 10 to 12.