KR20110082051A - Underlayer film for image formation - Google Patents

Abstract

식 중, A는 4가의 유기기를 나타내고, B는 하기 식(2) 또는 식(3)으로 나타내어지는 2가의 구조를 나타낸다.

An underlayer film for forming an image, comprising a polyimide precursor having a repeating structure represented by the following formula (1) or a polyimide obtained by dehydrating the polyimide precursor.

In the formula, A represents a tetravalent organic group, and B represents a divalent structure represented by the following formula (2) or formula (3).

Description

Underlayer Film for Image Formation

The present invention relates to an underlayer film for image formation, and also to an organic transistor fabricated using the above image forming underlayer film.

At present, the mask deposition method and the photolithography etching method are mainly used for pattern formation of an electrode or a functional thin film in the manufacturing process of an electronic device. In these conventional methods, problems such as difficulty in increasing the size of the substrate or complicated processes are pointed out.

Recently, for these conventional methods, it has been proposed to apply the separation coating technique using the difference in wettability of liquid to the patterning of functional thin films. This creates a patterning layer consisting of a liquid wetted area and a liquid hardly wetted area on the surface of the substrate, and a functional thin film is formed only in the wetted area by applying and drying a solution of the functional thin film forming material on the patterned layer. And electronic devices such as organic EL (electroluminescent) devices and organic FET (field effect transistor) devices.

As the functional thin film patterning layer, ultraviolet light is irradiated through a mask to a photocatalyst-containing layer made of titanium dioxide and organopolysiloxane (see Patent Document 1, for example), and a compound having a light absorption site such as a dye and a fluorine-containing polymer It is known to irradiate ultraviolet light to a layer consisting of laser light through a mask or a mask (see Patent Document 2, for example). Moreover, the method of forming the said patterning layer by depositing a fluorine-type coating agent through a mask is also proposed (for example, refer patent document 3).

The patterning layer proposed so far, such as the above patent document, remains in the device even if it serves as the patterning of the functional thin film. Therefore, the patterning layer needs durability for subsequent processes and reliability that does not adversely affect its characteristics even in an electronic device. Such necessary characteristics of the patterning layer vary depending on the device to be manufactured and the place of use of the patterning layer. Among them, the electrical insulating property is an important necessary characteristic in the patterning layer of the electrode.

In addition, the method proposed so far has focused only on the characteristic as a patterning layer. Therefore, for example, when patterning the source electrode and the drain electrode of the organic FET device, it is necessary to prepare a separate gate insulating film under the patterning layer.

On the other hand, polyimide is excellent in heat resistance, mechanical strength, electrical insulation, chemical resistance, etc., and is used in various electronic devices. As an example using polyimide as a patterning layer, what used the tetracarboxylic acid anhydride which has alicyclic structure (for example, refer patent document 4) is disclosed. However, in these examples, since the irradiation amount of ultraviolet rays was very large, a long exposure process was necessary.

Japanese Patent Application Laid-Open No. 2000-223270 Japanese Patent Application Laid-Open No. 2004-146478 Japanese Patent Application Laid-Open No. 2004-273851 Japanese Patent Laid-Open No. 2006-185898

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

The inventors of the present invention have made extensive efforts to achieve the above object, and as a result, by containing a thiol ester structure in the side chain of the polyimide precursor or the polyimide obtained from the polyimide precursor, It has been found that the water contact angle is greatly changed with a small exposure amount, and thus the present invention has been completed.

That is, the present invention includes a polyimide precursor having a repeating structure represented by the following formula (1) as a first point of view, or a polyimide obtained by dehydrating and closing the polyimide precursor. It is about.

(Wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2) or formula (3), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group). , 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 with a fluorine atom, and each 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 polyimide precursor obtained by reacting the tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride component represented by following formula (6), and the diamine component containing the diamine represented by Formula (7) by a 2nd viewpoint, or the said polyimide An underlayer film for image formation comprising a polyimide obtained by dehydrating and closing a mid precursor.

[Wherein, A represents a tetravalent organic group, and B represents 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 with a fluorine atom, and each 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).

In the third aspect, the lower layer film for image formation according to the first or second point of view, wherein Z in formula (2) or formula (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms in which any hydrogen atom is substituted with fluorine atom. It is about.

The fourth aspect relates to the underlayer film for image formation according to the first to third viewpoints in which A has an aliphatic ring or represents a tetravalent organic group composed of only aliphatic groups.

It relates to the underlayer film for image formation in any one of the 1st viewpoint thru | or a 4th viewpoint which shows the bivalent structure in which B is represented by Formula (2) as a 5th viewpoint.

It relates to the underlayer film for image formation in any one of the 1st thru | or 5th viewpoint which X and Y show a single bond by a 6th viewpoint.

A seventh aspect relates to an organic transistor having the image forming underlayer film according to any one of the first to sixth viewpoints.

From an 8th viewpoint, it is related with the diamine compound represented by following formula (14) or 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 in which any hydrogen atom is substituted with a fluorine atom, and each R independently represents a fluorine atom or 1 to 3 carbon atoms. An alkoxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3).

The 9th viewpoint relates to the polyimide precursor containing the repeating unit represented by following formula (1), or the polyimide obtained by dehydrating the said polyimide precursor.

(Wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2a) or formula (3a), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group). , 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 in which any hydrogen atom is substituted with a fluorine atom, and each R independently represents a fluorine atom or 1 to 3 carbon atoms. An alkoxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3).

The polyimide precursor obtained by reacting the tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride component represented by following formula (6), and the diamine component containing the diamine represented by Formula (7) by a 10th viewpoint, or the said polyis An image forming underlayer film coating liquid comprising a polyimide obtained by dehydrating and closing a mid precursor.

(In formula, A represents a tetravalent organic group, B represents Formula (2) or Formula (3).

Represents a divalent structure represented by R ¹ , R ² each independently represents 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 is 3 to 26 carbon atoms which may be substituted with fluorine atoms An aliphatic hydrocarbon of R, independently R 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 relates to an image forming underlayer film coating solution according to the tenth aspect, wherein Z in formula (2) or formula (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms in which any hydrogen atom is substituted with a fluorine atom.

In addition to the twelfth aspect, the present invention relates to an underlayer coating liquid for image formation according to the tenth or eleventh aspect, which comprises a soluble polyimide having an imidation ratio of 80% or more.

The thirteenth aspect relates to an image forming underlayer film obtained by firing the image forming underlayer film coating solution according to the tenth to twelfth viewpoints.

An organic transistor having a film obtained by firing the image forming underlayer film coating solution described in the tenth to thirteenth viewpoints from the fourteenth viewpoint.

The underlayer film for image formation of the present invention can change the surface of the film from hydrophobic to hydrophilic with a small amount of ultraviolet irradiation. Therefore, by using such a characteristic, image formation of functional materials, such as an electrode, becomes possible. This makes it possible to drastically shorten the process time in the manufacture of electronic devices, making it a very effective material in terms of productivity.

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the micrograph of the silver electrode on PI-4 produced in Example 9 (the line width of a silver electrode is 100 micrometers).
FIG. 2 is a view showing a micrograph of the silver electrode on the composition A prepared in Example 10 (the line width of the silver electrode is 100 µm).
3 is a diagram showing current-voltage characteristics in a nitrogen atmosphere of a polyimide film obtained by firing a polyimide precursor (PI-1) (Examples 11 and 12).
4 is a diagram showing current-voltage characteristics in the atmosphere of the polyimide film obtained by firing the polyimide precursor (PI-1) (Examples 11 and 12).
FIG. 5 is a diagram showing current-voltage characteristics in the atmosphere of the polyimide film prepared in Examples 13 to 16. FIG.
FIG. 6 is a diagram showing transfer characteristics of an organic transistor obtained by irradiating 2J / cm 2 of ultraviolet light to a film obtained from PI-4 (electrode) (Example 17).
FIG. 7 is a diagram showing the transfer characteristics of an organic transistor obtained by irradiating 2J / cm 2 of ultraviolet light to a film obtained in Composition A (Example 18).
FIG. 8 is a diagram showing the transfer characteristics of an organic transistor obtained by irradiating 1J / cm 2 ultraviolet-ray to a film obtained from PI-4 (Example 19).

The present invention is a novel image forming underlayer film containing a polyimide precursor having a thiol ester bond in a side chain or a polyimide obtained from the polyimide precursor. The present invention also relates to an organic transistor using the image forming film.

Hereinafter, it demonstrates in detail.

[Polyimide Precursor] The present invention is an underlayer film for forming an image comprising a polyimide precursor having a repeating structure represented by the following formula (1) or a polyimide obtained by dehydrating and closing the polyimide precursor.

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

In said Formula (1), R <^1> , R <^2> represents a hydrogen atom or monovalent organic group, respectively, and a C1-C4 alkyl group is mentioned as a specific example of monovalent organic group, for example.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and t-butyl group.

Among these, it is preferable that R <^1> and R <^2> are hydrogen atoms.

In the formula (1), the structure of the organic group represented by A is not particularly limited as long as it is a tetravalent organic group. In addition, the polyimide precursor may have a structure represented by one or a plurality of formulas (1). Therefore, in the polyimide precursor, the structure of the organic group represented by A may be one type, or multiple types may be mixed. Especially, it is preferable that A is a tetravalent organic group which has an aliphatic ring or consists only of aliphatic. More preferably, it is a tetravalent organic group which has an aliphatic ring.

As a preferable specific example of the organic group represented by A, the organic group of following formula A-1-A-46 is mentioned.

Formulas A-1 to A-46 may be appropriately selected according to properties required when the underlayer film for image formation is used.

For example, in the above formulas A-1 to A-46, as the tetravalent organic group in which the exposure sensitivity (in the present specification, the exposure sensitivity represents the degree of conversion from hydrophobicity to hydrophilicity per exposure amount (ultraviolet radiation dose)) is improved, the expression A is represented by Formula A. The tetravalent organic group which has an aliphatic ring of -1 to A-25 or consists only of aliphatic is mentioned, Especially, A-1, A-6, A-16, or A-19 is mentioned as an organic group with high effect.

Moreover, the tetravalent organic group of Formula A-1-A-25 is also preferable from a viewpoint of the effect which raises insulation.

In the formula (1), when groups other than the formulas A-1 to A-25 are mixed in the organic group represented by A, the ratio of the formulas A-1 to A-25 is preferably 10 mol% or more, and 50 More than mol% is more preferable, and more than 80 mol% is the most preferable.

In said Formula (1), B represents the bivalent structure which has a thiol ester bond in a side chain, as shown by following formula (2) or Formula (3).

By containing a thiol bond in the side chain of the polyimide precursor (or polyimide obtained thereby) including the repeating structure represented by Formula (1), when the thiol ester group is photolyzed, the side chains bound through the thiol ester group are cleaved from the polymer main chain. do. Therefore, it can be expected that the hydrophilicity of the side chains bound through thiol bonds leads to changes in hydrophilicity by light irradiation such as ultraviolet rays.

In said formula (2) or (3), X represents a single bond or a bivalent aromatic group of 6-20 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 arbitrary hydrogen atoms may be substituted with fluorine atoms.

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 structure of B represented by said Formula (2) or (3) may contain aromatic carbocyclic ring in a side chain structure from a viewpoint of improving the absorption efficiency of an ultraviolet-ray.

Therefore, in said Formula (2) or (3), when X represents a bivalent aromatic group of 6-20 carbon atoms, a preferable aromatic group is a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, and anthracenylene group Etc. can be mentioned.

Examples of the aliphatic hydrocarbon group having 3 to 26 carbon atoms in Z include propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, sec-nonyl and isononyl Linear or branched alkyl groups such as decyl, dodecyl, tetradecyl, hexadecyl and octadecyl; Alkenyl groups such as allyl and hexenyl; Alicyclic hydrocarbon groups having cyclobutane, cyclopentane, cyclohexane, cyclodecane, steroid skeleton, adamantane and the like; ethyl formate, methyl acetate, ethyl acetate, methyl propionate, diacetyl, methyl isobutyrate, ethyl iso Butyrate, ethyl butyrate, propyl butyrate, isobutyl acetate, isobutyl isobutyrate, isobutyl butyrate, isobutyl isovalerate, isoamyl acetate, isoamyl propionate, amyl propionate, amyl isobutyrate, amyl butyrate, amyl Ester groups of isovalerate, allyl hexanoate, ethyl acetoacetate, ethyl heptylate, heptyl acetate, ethyl octylate, styryl acetate, nonyl acetate, boronil acetate, diethyl phthalate, and the like. To straight chain alkyl groups of 26 Is recommended.

The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 3 to 26 carbon atoms, in which any hydrogen atom may be substituted with a fluorine atom, and preferably any hydrogen atom is substituted with a fluorine atom, particularly preferably straight chain fluorine having 4 to 7 carbon atoms. It is a roalkyl group.

As a preferable specific example of the structure of B represented by said Formula (2) or (3), the structure shown to following [B-1]-[B-17] is mentioned. Among these divalent structures, the divalent structures shown in [B-13] to [B-17] are particularly preferable from the viewpoint of facilitating the improvement of hydrophobicity, and more preferably [B-15] to [B-17]. It is a bivalent structure shown in.

In addition, polyimide precursors (and polyimides obtained therefrom) used in the underlayer film for forming an image of the present invention are considered when other properties, such as insulation, solvent solubility, film-forming property, and film adhesion, are also important properties. In addition to the structure represented by said Formula (1), the divalent organic group B in said Formula (1) is following Formula (4) substituted by the other divalent organic group D which does not have a thiol ester bond in a side chain. The polyimide precursor (and polyimide obtained from this) containing the structure shown may be sufficient.

In this case, the structure shown by the said Formula (1) containing the bivalent organic group B which has a thiol ester bond in a side chain, and the structure of Formula (4) containing the other divalent organic group which does not have a thiol ester bond in a side chain. The bond with may be either a block bond and / or a random bond.

In formula, A, R <^1> and R <^2> are the same as the definition in said Formula (1), m shows a natural number, D shows the other bivalent structure which does not have a thiol ester bond in a side chain.

In the polyimide precursor (and polyimide obtained therefrom) used in the underlayer film for image formation of the present invention, in the formula (4), when D has a long chain alkyl group in the side chain, the structure represented by the formula (4) (side chain If the content ratio of the structure having no thiol ester bond) is too high, the sensitivity to ultraviolet rays is reduced. Therefore, when including the structure represented by Formula (4), it is preferable to make ratio of the structure represented by Formula (1) (structure which has a thiol ester bond in a side chain) 30 mol% or more.

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

In addition, in Formula (4), when D does not have a long-chain alkyl group in a side chain, since hydrophobicity of a film is mainly influenced by the ratio of the structure represented by Formula (1), surface tension of an image forming liquid and adhesiveness with an upper layer member. What is necessary is just to determine the ratio of the structure represented by Formula (1) in consideration of etc.

In the structure represented by the formula (2) or (3), when a part of the aliphatic hydrocarbon group of Z is substituted with a fluorine atom, the ratio of the structure represented by the formula (1) is high even if it is 10 mol% or less. Hydrophobicity and sensitivity can be obtained. In other words, it is believed that the change in hydrophilicity of the film is caused by decomposition and separation of the side chain structure, and the exposure sensitivity does not necessarily decrease even 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 preferably has a structure having high insulating properties, and specific examples thereof include the structures of the following [D-1] to [D-57]. Can be mentioned.

In the following [D-1]-[D-57], the structure of [D-1]-[D-5] is preferable at the point which insulation property improves easily.

Moreover, as a structure with a high effect of improving solvent solubility, [D-2], [D-5], [D-7], [D-8], [D-12], [D-22], and [D] -24] to [D-27] and [D-29].

Moreover, although the structure of [D-55]-[D-57] is mentioned as a specific example of hydrophobic structure which has a long-chain alkyl group in a side chain, they can expect insulation improvement by the characteristic of an organic transistor, and a sensitivity does not fall. It can be used in the range, and when using it, care should be taken in its usage ratio.

The polyimide precursor described above is produced by, for example, polymerizing tetracarboxylic dianhydride and its derivatives with diamine. It is preferable that it is a polyimide precursor (polyamic acid) represented by following formula (5) from the reason which can be obtained relatively simply by making tetracarboxylic dianhydride component and a diamine component react especially as a raw material.

(In formula, A, B, and n are the same as the definition in Formula (1).)

`` Tetracarboxylic dianhydride and its derivatives ''

Although tetracarboxylic dianhydride and its derivative (s) are not specifically limited in this invention, It is preferable to use the tetracarboxylic dianhydride represented by following formula (6). A in Formula is the same as that of the definition of Formula (1) mentioned above, The specific example is what was shown to Formula A-1-A-46 mentioned above.

(In formula, A is the same as the definition in Formula (1).)

As described so far, the structure of the organic group represented by A in the polyimide precursor may be one kind or a plurality of kinds thereof may be mixed. Especially, it is preferable that A is a tetravalent organic group which has an aliphatic ring or consists only of aliphatic, More preferably, it is a tetravalent organic group which has an aliphatic ring. Therefore, it is preferable that the tetracarboxylic dianhydride component contains many compounds of the formula (6) in which A has an aliphatic ring or a tetravalent organic group composed only of aliphatic groups. More preferably, A contains many compounds of the formula (6) which is a tetravalent organic group which has an aliphatic ring.

When a polyimide precursor or the like is produced using only an aromatic acid dianhydride and used as an underlayer film for forming an image, when a high electric field is applied to the underlayer film for forming an image, there is a tendency that the insulation is remarkably lowered. On the contrary, when the aliphatic dianhydride is used, the insulation in the high system is excellent.

For example, the operating voltage of the organic transistor may be about 1 MV / cm. In this case, it is preferable to use an aliphatic dianhydride as a raw material of the polyimide precursor from the standpoint of insulation.

<< diamine >>

The diamine used for a diamine component in this invention is represented by following formula (7), B is a structure represented by following formula (2) or following formula (3), ie, a bivalent structure which has a thiol ester bond in a side chain. As a specific example of B, the structure shown to [B-1]-[B-17] mentioned above is mentioned.

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 represents} COO- or -CH ₂ CH ₂ COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted with a fluorine atom, and R independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon source An alkyl group of embroidery 1 to 3, and t represents an integer of 0 to 3.)

Moreover, in addition to the diamine represented by Formula (7), diamines other than Formula (7) represented by Formula (Q1) can also be used together in the range in which the effect of this invention is expressed.

In formula (Q1), D is the same as the definition in said formula (4). Therefore, as a specific example of the diamine represented by Formula (Q1), the diamine which has the bivalent structure in which the structure of D is shown to [D-1]-[D-57] mentioned above is mentioned.

[Synthesis method of diamine compound]

The method of obtaining the diamine whose B is a structure of Formula (2) among the diamine represented by said Formula (7) is not specifically limited. As an example, it can be obtained by synthesizing the corresponding dinitro compound represented by the following general formula (8), reducing the nitro group and converting it to an amino group. The method of reducing the dinitro compound is not particularly limited, and typically palladium-carbon, platinum oxide, Raney nickel, iron, tin chloride, platinum black, rhodium-alumina, etc. are used as a catalyst and ethyl acetate, toluene, tetrahydrofuran, di There is a method performed by a reaction using a solvent such as oxane or alcohol, hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride or the like. Compounds having sulfur atoms or the like in the backbone of the dinitro compound are sometimes catalytic poisons and may deactivate the catalyst, so it is more preferable to use a chemical reduction method using Raney nickel, iron, tin chloride and the like.

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

The dinitro compound of the formula (8) can be obtained by the reaction of the dinitrobenzoyl chloride (9) and the thiol group-containing compound (10) shown below.

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

The method of obtaining the diamine whose B is a structure of Formula (3) among the diamine represented by said Formula (7) is not specifically limited. For example, after synthesize | combining the dinitro compound represented by following formula (11), it can obtain by reducing a nitro group and converting to an amino group like the case of the said dinitro compound (8).

(Wherein X, Y, Z, R and t are as defined in formula (3).)

The dinitro compound of the formula (11) can be obtained by reaction with a thiol group-containing dinitro compound (12) shown below and an acid chloride (13) having an aliphatic hydrocarbon which may contain a fluorine atom.

(Wherein X, Y, Z, R and t are as defined in formula (3))

<< Production method of polyimide precursor >>

In order to obtain a polyimide precursor having a repeating structure represented by formula (1), a tetracarboxylic dianhydride component comprising a tetracarboxylic dianhydride represented by formula (6) and a diamine represented by formula (7) and As needed, the method of mixing and reacting the diamine component containing the diamine component represented by said Formula (Q1) in an organic solvent is simple.

As a method of mixing the tetracarboxylic dianhydride component and the diamine component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred to disperse or dissolve the tetracarboxylic dianhydride component intact or dissolved in an organic solvent. On the other hand, the method of adding a diamine component to the solution which disperse | distributed or dissolved the tetracarboxylic dianhydride component in the organic solvent, the method of adding the tetracarboxylic dianhydride component and a diamine component alternately, etc. are mentioned.

Moreover, in the case of the compound in which two or more types of tetracarboxylic dianhydride component and a diamine component exist, you may carry out polymerization reaction in the state which mixed these multiple types of components previously, and may carry out polymerization reaction individually in order.

When polymerizing the polyimide precursor used in the present invention, the compounding ratio of tetracarboxylic dianhydride component and diamine component, i.e., <total mole number of tetracarboxylic dianhydride component>: <total mole number of diamine component> is 1: 0.5 It is preferable that it is from 1: 1.5. As in the conventional polycondensation reaction, as the molar ratio approaches 1: 1, the degree of polymerization of the resulting polyimide precursor increases and the molecular weight increases.

In the method for producing the polyimide precursor, the temperature when 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.

If the reaction temperature is set to a high temperature, the polymerization reaction proceeds quickly and is completed, but if it is too high, a high molecular weight polyimide precursor may not be obtained.

In the polymerization reaction carried out in an organic solvent, the solid content concentration of the amphoteric component (the total mass of the tetracarboxylic anhydride component and the diamine component) in the solvent is not particularly limited, but if the concentration is too low, a high molecular weight polyimide precursor is obtained. When the concentration is too high, the viscosity of the reaction solution becomes so high that it becomes difficult to stir uniformly. Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. In the initial stage of the polymerization reaction, it may be carried out at a high concentration, followed by purification of the polymer (polyimide precursor), and then an organic solvent may be added.

The organic solvent used in the polymerization reaction is not particularly limited as long as the produced polyimide precursor is dissolved. Examples thereof include N, N-dimethylformamide, N, N-dimethylformacetamide, and N-methyl-2. -Pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma -butyrolactone, etc. are mentioned. You may use these individually or in mixture of 2 or more types. Moreover, the solvent which does not melt a polyimide precursor may be sufficient, and you may mix with the said solvent in the range in which the produced polyimide precursor does not precipitate.

The solution containing the polyimide precursor obtained in this way can be used as it is for the preparation of the image forming underlayer film coating solution described later. In addition, the polyimide precursor may be precipitated and isolated in poor solvents such as water, methanol, and ethanol to be recovered and used.

[Polyimide]

The polyimide precursor having the structures represented by the formulas (1) and (4) (and the formula (5)) can form a polyimide by dehydration ring. Although the method of the said imidation reaction is not specifically limited, Catalytic imidation using a basic catalyst and an acid anhydride is preferable because the molecular weight fall of a polyimide does not easily occur at the time of imidation reaction, and imidation rate is easy to control.

Catalytic imidization is possible by stirring the polyimide precursor in an organic solvent for 1 to 100 hours in the presence of a basic catalyst and an acid anhydride.

In addition, here, the polyimide precursor may use the solution containing the polyimide precursor obtained by superposition | polymerization of the tetracarboxylic dianhydride component and diamine component mentioned above as it is (isolated).

Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Among these, pyridine is preferable because it has a basicity suitable for advancing reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride and pyromellitic anhydride. Among these, acetic anhydride is preferable because purification of the polyimide obtained after the end of imidation becomes easy.

As an organic solvent, the solvent used at the time of the polymerization reaction of the polyimide precursor mentioned above can be used.

As for reaction temperature at the time of catalyst imidation, -20-250 degreeC is preferable, More preferably, it is 0-180 degreeC. If the reaction temperature is set to a high temperature, imidization proceeds quickly, but if it is too high, the molecular weight of the polyimide may decrease.

The amount of the basic catalyst is preferably 0.5 to 30 mole times, more preferably 2 to 20 mole times, relative to the acid amide group in the polyimide precursor. The amount of the acid anhydride is preferably 1 to 50 mol times, more preferably 3 to 30 mol times with respect to the acid amide group in the polyimide precursor.

The imidation ratio of the polyimide obtained by adjusting the said reaction temperature and catalyst amount can be controlled.

The reaction solution of the solvent-soluble polyimide obtained as described above can be used for the preparation of the gate insulating film described later as it is, but since the reaction solution contains an imidization catalyst and the like, it is preferable to use a purified, recovered and washed polyimide. desirable.

The recovery of the polyimide is easy by the method of precipitating the polyimide by adding the reaction solution to the poor solvent being stirred and filtering it.

Although it does not specifically limit as a poor solvent used at this time, Methanol, hexane, heptane, ethanol, toluene, water, etc. can be illustrated. After the precipitate is collected by filtration, washing with the poor solvent is preferred.

The recovered polyimide can be dried under normal pressure or under reduced pressure to produce polyimide powder.

If the polyimide powder is further dissolved in a good solvent and reprecipitated in a poor solvent 2 to 10 times, the impurities in the polymer may be further reduced.

The good solvent used at this time is not particularly limited as long as the polyimide precursor or polyimide can be dissolved. Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, and N. -Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, γ-butyrolactone Etc. can be mentioned.

Moreover, when three or more types of poor solvents, such as alcohol, ketones, and a hydrocarbon, are used as a poor solvent used for reprecipitation, further refinement | purification efficiency will become high.

[Image forming underlayer coating liquid]

The underlayer film for image formation of the present invention can be formed using an image forming underlayer film coating liquid. The image forming underlayer film coating liquid is a coating liquid containing the polyimide precursor, the polyimide, and a solvent, which may further contain a coupling agent or a surfactant described later, preferably in the following formula (6) Polyimide precursor obtained by reacting the tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the following, and the diamine component containing the diamine represented by Formula (7), or the polyimide obtained by dehydrating the said polyimide precursor. It is a coating liquid containing.

(In formula, A represents a tetravalent organic group, B represents Formula (2) or Formula (3).

Represents a divalent structure represented by R ¹ , R ² each independently represents 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 is 3 to 26 carbon atoms which may be substituted with fluorine atoms An aliphatic hydrocarbon of R, independently R 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).

Especially preferably, Z of said Formula (2) or Formula (3) is an image forming underlayer film coating liquid which shows the C3-C26 aliphatic hydrocarbon group in which arbitrary hydrogen atoms are substituted by the fluorine atom.

The molecular weight of the polyimide precursor and / or polyimide used in the image forming underlayer film coating solution described above is the weight of polyethylene glycol (or polyethylene oxide) in terms of stability such as ease of handling and solvent resistance during film formation. As average molecular weight (measurement result by GPC), 2,000-200,000 are preferable, It is preferable to use what is 5,000-50,000 more preferably.

When the underlayer film for image formation was produced using the above-described image forming underlayer coating liquid and irradiated with ultraviolet rays, the underlayer film for image formation obtained because there was no significant difference between the polyimide precursor and the polyimide with respect to the amount of hydrophilic change. In the case of focusing on the point, the imidation ratio is not particularly limited.

However, by using polyimide, it is possible to obtain a highly reliable film with low temperature firing (180 ° C or less) that a plastic substrate can cope with. Polyimide has a lower polarity than polyimide precursors and can increase the water contact angle before UV irradiation. It is more preferable to use polyimide from the point that the advantages, such as (the hydrophobicity can be improved), can be acquired.

On the other hand, when the above-mentioned image forming underlayer coating liquid is used for an image forming underlayer film (for example, a gate insulating film) which focuses on insulation, it is preferable that the imidation ratio of this coating liquid is 90% or more. However, if solvent solubility is impaired, the imidation ratio may be lowered. In this case, however, high insulation of the lower layer may be maintained by high imidization (high insulation) of the lowermost layer using a blend method described below when forming the film. It is useful because.

The solvent used in the above-described image forming underlayer coating liquid is not particularly limited as long as it can dissolve the polyimide precursor or polyimide, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, 2- Pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, Good solvents, such as (gamma) -butyrolactone, are mentioned. These may be used individually by 1 type, or may be used in mixture, and also may mix and use the poor solvents, such as alcohol, ketones, and a hydrocarbon, with the said good solvent.

The ratio of solids in the above-described image forming underlayer film coating liquid is not particularly limited as long as each component is uniformly dissolved in a solvent, including a coupling agent and the like described later. For example, it is 5-20 mass%. Herein, the solid content means that the solvent is removed from all components of the image forming underlayer coating liquid.

The method for preparing the above-described image forming underlayer film coating solution is not particularly limited, but the solution containing the polyimide precursor obtained by the polymerization of the tetracarboxylic anhydride component and the diamine component described above or the reaction solution of the polyimide obtained using the above solution. You can use as is.

In addition, in the above-described image forming underlayer coating liquid, a coupling agent may be further contained as long as the effect of the present invention is not impaired for the purpose of improving the adhesion between the coating liquid and the substrate.

Examples of the coupling agent include a functional silane-containing compound and an epoxy group-containing compound, specifically 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-amino Propyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxy Silane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-trimethoxysilyl Propyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triaza Decane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-dia Zanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-amino Propyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 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 diglycid Dyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 6- tetraglycidyl-2,4-hexanediol, N, N, N ', N'- Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl- And compounds such as 4,4'-diaminodiphenylmethane.

These may be used individually by 1 type, or may be used in combination of 2 or more type.

When using the said coupling agent, it is preferable to add the content at 0.1-30 mass parts with respect to 100 mass parts of image forming underlayer film coating liquid, More preferably, it is 1-20 mass parts.

Furthermore, the above-mentioned image forming underlayer film coating liquid may contain a surfactant for the purpose of improving the coating property of this coating liquid, the film thickness uniformity and the surface smoothness of the film obtained from this coating liquid.

Although it does not restrict | limit especially as said surfactant, For example, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant etc. are mentioned. As this kind of surfactant, for example, EFTOP EF301, EF303, EF352 (manufactured by Jemco Inc), megafac F171, F173, R-30 (manufactured by Dainippon Inky Chemical Co., Ltd.), fluorad FC430, FC431 (Sumitomo 3M) Limited), Asahi Guard AG710, surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.) etc. are mentioned.

When using the said surfactant, the content becomes like this. Preferably it is 0.01-2 mass parts, More preferably, it is 0.01-1 mass part with respect to 100 mass parts of polymer components contained in an image formation lower layer film coating liquid.

[About polymer blend]

The above-described image forming underlayer coating liquid may be mixed with the above-described polyimide precursor or polyimide with another polymer capable of forming a film (for example, a highly insulating polymer) to take the form of a so-called polymer blend.

By appropriately adjusting the structure of the polymer (polyimide precursor, polyimide, and other polymers) contained in the polymer blend, the concentration gradient of each polymer can be generated in the thickness direction of the film when the underlayer film for image formation is formed. It can be used as a useful means.

For example, since the film surface mainly causes the change of hydrophilicity, from this point of view, the polyimide precursor and / or polyimide having a thiol ester bond in the above-described side chain may only exist in the upper layer (surface layer) of the underlayer film for image formation. .

Therefore, in the case where the image forming underlayer film coating liquid is in the form of a polymer blend (hereinafter, the coating liquid in this form is called a blend coating liquid), the blending ratio of the polyimide precursor or polyimide described above is the blend coating liquid. It is 1 mass%-100 mass% in solid content of. If it is 1 mass% or less, when this blend coating liquid is formed into a film, it will become difficult to completely cover the outermost surface of a film, and there exists a possibility that image formation ability may deteriorate.

The polymer blend is useful, for example, in the case of using the above-described image forming underlayer coating liquid for a gate insulating film application requiring particularly high insulating properties.

When used as a gate insulating film, the coating solution is compatible with a firing temperature of 180 ° C. or below, can be formed by coating, solvent resistance to organic semiconductor coating liquid (nonpolar solvents such as xylene and trimethylbenzene), and low water absorption. Although many characteristics, such as, are required, especially the required performance regarding insulation is high. In order to achieve the high insulation, the imidization ratio of the above-mentioned image forming underlayer coating liquid may be at least 80%, in some cases, at least 90%. On the other hand, if the imidation ratio exceeds 90%, Loss of solvent solubility At this time, by placing the high insulating layer only on the lowermost layer of the insulating film and placing the layer of the above-described image forming lower layer coating liquid on the upper layer, the high insulating property of the insulating film can be maintained and the problem of solubility can be solved.

As described above, in order for the lower layer of the image forming lower layer film to be a high insulating layer and the upper layer to be a hydrophilic conversion layer, these layers may be laminated in order, but the operation is complicated.

At this time, the material of the high insulating layer and the material of the hydrophilic conversion layer (that is, the above-described polyimide precursor and / or polyimide) are mixed, and at this time, if the polarity or molecular weight of the upper layer material is smaller than that of the lower layer, the mixed liquid The above-described concentration gradient (layer separation referred to here) can be easily controlled because the above-described concentration gradient (layer separation referred to here) can be easily controlled because the material of the upper layer moves to the surface to form a layer while the solvent is evaporated.

Soluble polyimide is most preferred as a material for forming a highly insulating film capable of forming the underlayer. When soluble polyimide is used as the underlayer, the imidation ratio of the polyimide in the solution is preferably high, at least 50%, preferably 80%, most preferably 90% from the standpoint of insulation.

Other materials that can be used as the lower layer material include general organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinylphenol, polyisobutylene, polymethyl methacrylate and the like.

Preferred soluble polyimides include soluble polyimides composed of one or a plurality of structures selected from the group consisting of the structures of formula (16).

(Wherein A represents a tetravalent organic group consisting of an aliphatic ring or aliphatic, and D represents a divalent organic group)

The molecular weight of the soluble polyimide is preferably 2,000 to 200,000, more preferably 5,000 to 50,000 in terms of weight average molecular weight (measured by GPC) in terms of polyethylene glycol (or polyethylene oxide).

In Formula (16), the tetravalent organic group chosen from A-1 to A-25 is mentioned as a specific example of A, D-1-D-57 is mentioned as a specific example of D. Among these, the structure of A which is particularly preferable in view of high solubility of the soluble polyimide is A-5, A-6, A-16, A-18, A-19, A-20, A-21, A-22, It is a tetravalent organic group of A-25, and the structure of D is D-7, D-8, D-9, D-12, D-19, D-20, D-22, D-29, D-39, It is a divalent organic group of D-41 and D-42.

Such soluble polyimide may be used singly or in combination of a plurality.

In addition, when the polymer blend is used, for example, for an organic transistor or the like requiring a film thickness of about 400 nm, the polymer blend of the above-described polyimide precursor and / or polyimide required to have an upper layer (hydrophilic conversion layer) The content ratio in this should just be 1 mass% or more. If too small, unevenness in surface of the lower layer film surface property for image formation may become large. Preferably it is 5 mass% or more.

[Manufacturing method of coating and underlayer film for image formation]

The above-described image forming underlayer coating liquid is applied to a general plastic substrate or glass substrate such as polypropylene, polyethylene, polycarbonate, polyethylene terephthalate, polyether sulfone, polyethylene naphthalate, polyimide, or the like by a dipping method, spin coating method, The coating film can be formed by applying a transfer printing method, a roll coating method, an inkjet method, a spray method, a brush method, or the like, and preliminarily drying in a hot plate or an oven. Thereafter, the coating film is heat-treated to form an underlayer film for forming an image and an underlayer film for forming an insulating film.

Although it does not specifically limit as a method of the said heat processing, The method of performing in a suitable atmosphere using a hotplate or oven, ie, inert gas, such as air | atmosphere and nitrogen, in vacuum, etc. can be illustrated.

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

Firing may give two or more temperature changes. The uniformity of the film | membrane obtained by baking in steps can be improved more.

Further, when the underlayer film for forming an image is formed, the image forming underlayer coating liquid is a form containing a polyimide precursor and / or a polyimide and the above-described solvent, so that it can be used for application to a substrate as it is, but for concentration adjustment or You may use it as a coating liquid by adding the solvent mentioned above and other various solvents for the purpose of ensuring the flatness of a coating film, the improvement of the wettability to the board | substrate of a coating liquid, the adjustment of the surface tension, polarity, and boiling point of a coating liquid.

Specific examples of such a solvent include, in addition to the solvent described in the above paragraph, ethyl-cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and the like. 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, 2- (2-methoxypropoxy) propanol, 2- (2-ethoxypropoxy) propanol and 2- ( Lactic acid derivatives such as propylene glycol derivatives such as 2-butoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester and the like. These may be used alone or in combination.

In addition, from the viewpoint of improving the storage life of the coating liquid and the film thickness uniformity of the coating film, 20 to 80% by mass of the exclusive medium is N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pi. It is preferable to set it as at least 1 sort (s) of solvent chosen from a rollidone, (gamma) -butyrolactone, and dimethyl sulfoxide.

Although the density | concentration of a coating liquid does not have a restriction | limiting in particular, 0.1-30 mass% is preferable as solid content concentration of a polyimide precursor and a polyimide, More preferably, it is 1-10 mass%. These are arbitrarily set according to the specification of the coating device and the film thickness to be obtained.

When the underlayer film for forming an image of the present invention produced as described above is used as the underlayer film for image forming, when the film thickness is too thin, the patterning property after ultraviolet irradiation decreases, and when too thick, the surface uniformity is impaired. Therefore, as this film thickness, 5 nm-1000 nm are preferable, More preferably, they are 10 nm-300 nm, Most preferably, they are 20 nm-100 nm.

In addition, the underlayer film for image formation of the present invention may function as an insulating film when the insulating property is sufficiently high. In this case, the underlayer film for image formation is used as a gate insulating film, for example, on a direct gate electrode in an organic FET device. At this time, the film thickness of the lower layer film for image formation is intended to ensure insulation, and is preferably thicker than the case where the lower layer film for image forming is used. The film thickness is preferably 20 nm to 1000 nm, more preferably 50 nm to 800 nm, and most preferably 100 nm to 500 nm.

[Method of Manufacturing Electrode for Image Formation]

An image forming electrode can be manufactured by irradiating an ultraviolet-ray with a pattern shape to the underlayer film for image formation of this invention, and apply | coating the image forming liquid mentioned later.

In the present invention, a method of irradiating ultraviolet light in a pattern shape to the underlayer film for forming an image is not particularly limited. Etc. can be mentioned.

The material and the shape are not particularly limited as the mask, and the area requiring the electrode may transmit ultraviolet light, and the other area may not pass through the ultraviolet light.

At this time, the wavelength of the ultraviolet rays to be used is generally in the range of 200 nm to 500 nm, and it is preferable to select and use the wavelength of the ultraviolet rays appropriately according to the type of the image forming underlayer film to be used. Specifically, wavelengths, such as 248 nm, 254 nm, 303 nm, 313 nm, and 365 nm, are mentioned. Especially preferably, they are 248 nm and 254 nm.

The underlayer film for image formation of the present invention gradually increases its surface energy by irradiation with ultraviolet rays and saturates with a sufficient dose. The increase in the surface energy causes a drop in the contact angle of the image forming liquid, and as a result, the wettability of the image forming liquid in the ultraviolet irradiation part is improved.

Therefore, when the image forming solution is applied onto the image forming lower layer film of the present invention after UV irradiation, the image forming solution forms a pattern in a self-organizing manner according to the pattern shape formed by the difference in surface energy on the image forming lower layer film. A patterned electrode of can be obtained.

For this reason, although the amount of ultraviolet rays irradiated to the underlayer film for image formation needs to be irradiated with an amount in which the contact angle of the image forming liquid is sufficiently changed, it is preferable that it is 20 J / cm 2 or less in terms of energy efficiency and time reduction of the manufacturing process, It is more preferable that it is 10 J / cm <2> or less, and it is most preferable that it is 5 J / cm <2> or less.

In addition, the larger the difference between the contact angles of the image forming liquids in the ultraviolet irradiating portion and the unirradiating portion of the underlayer film for image forming, the easier the patterning becomes, and the electrode can be processed into a complex pattern or a fine pattern shape. Therefore, it is preferable that the change amount of the contact angle by ultraviolet irradiation is 5 degrees or more, It is more preferable that it is 10 degrees or more, It is most preferable that it is 20 degrees or more.

For the same reason, it is preferable that the contact angle of the image forming liquid is 30 degrees or more in the non-ultraviolet irradiation portion and 20 degrees or less in the ultraviolet irradiation portion.

In addition, since the solvent of the image forming solution is often used in water, in the performance evaluation of the underlayer film, the amount of change in the contact angle of the image forming solution may simply be changed to the amount of change in the contact angle of water.

In the present invention, the image forming liquid is a coating liquid which can be used as a functional thin film by applying a substrate to a substrate and then evaporating the solvent contained therein. For example, the charge transport material is dissolved or uniformly dispersed in at least one solvent. It can be mentioned. Here, charge transportability means the same meaning as conductivity, and means any one of hole transportability, electron transportability, positive charge transportability of holes and electrons.

The charge transport material is not particularly limited as long as it has a conductivity capable of transporting holes or electrons. Examples thereof include fine metal particles such as gold, silver, copper and aluminum, inorganic materials such as carbon black, fullerenes and carbon nanotubes, and organic materials such as polythiophene, polyaniline, polypyrrole, polyfluorene and derivatives thereof. (pi) conjugated polymer; and the like.

In addition, halogen, Lewis acid, protonic acid, and transition metal compounds (specific examples of Br ₂ , I ₂ , Cl ₂ , FeCl ₃ , MoCl ₅ , BF ₃ , AsF ₅₎ Charge-soluble materials such as, SO ₃ , HNO ₃ , H ₂ SO ₄ , polystyrenesulfonic acid, etc. or alkali metals, alkylammonium ions (specific examples include Li, Na, K, Cs, tetraethyleneammonium, tetrabutylammonium, etc.) The charge donor substance may be further added to the image forming liquid as a dopant.

The solvent for the image forming solution is not particularly limited as long as the charge transport material or the dopant is dissolved or uniformly dispersed. However, from the viewpoint of obtaining an accurate electrode pattern, water and various alcohols are preferable because it is preferable that the damage to the underlayer film for image formation of the present invention is small while showing a sufficiently large contact angle with respect to the unirradiated portion of the underlayer film for image formation.

Furthermore, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2- Polar solvents such as pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide and tetramethyl urea also have excellent solubility in organic charge transport materials and exhibit a sufficiently large contact angle with respect to the non-irradiated portion of the underlayer film for image formation. Although it is preferable to use these, it is preferable to use in the range with little damage to the underlayer film for image formation of this invention.

The concentration of the charge-transporting substance in the image forming liquid is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, most preferably 1 to 5% by mass.

Specific examples of the image forming solution according to the present invention include Baytron (registered trademark) P (polyethylene dioxythiophene, manufactured by Bayer AG).

The electrode according to the present invention is produced by applying the image forming liquid on the underlayer film for image formation of the present invention, and patterning and evaporating the solvent. The solvent evaporation method is not particularly limited, but a uniform film formation surface can be obtained by evaporating in a suitable atmosphere using a hot plate or an oven, that is, in an inert gas such as air, nitrogen, or vacuum.

Although the temperature which evaporates a solvent is not specifically limited, It is preferable to carry out at 40-250 degreeC. In view of maintaining the pattern shape and achieving uniformity of the film thickness, two or more temperature changes may be provided.

The electrodes made of the image forming solution are used not only as wirings for connecting electronic devices but also as electrodes for electronic devices such as field effect transistors, bipolar transistors, various diodes, and various sensors.

The electronic device according to the present invention has the electrode of the present invention.

Although the example which used the image forming lower layer film of this invention for the organic FET element is shown below, this invention is not limited to this.

First, a highly dope n-type silicon substrate is prepared. It is preferable that the substrate is washed with a liquid by detergent, alcohol, pure water or the like beforehand to be purified, and subjected to surface treatment such as ozone treatment or oxygen-plasma treatment immediately before use. SiO ₂ , Ta ₂ O ₅ , Al ₂ O ₃ , and the like are deposited 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 layer varies depending on the use of the organic FET, but is preferably in the range of 30 nm to 1000 nm because it serves both as a driving voltage and electrical insulation.

Next, a polyimide precursor having a repeating structure represented by the general formula (1) and / or a layer containing polyimide is formed on the insulating film in the above-described order. The film thickness of the layer is most preferably set to 20 nm to 100 nm. Thereafter, ultraviolet rays are irradiated by using a mask or the like so as to obtain a desired electrode shape.

Then, an image forming solution using a polar solvent such as water is applied to the lower layer film surface for image forming. The applied image forming solution is spread quickly and stabilized on the hydrophilic portion (ultraviolet ray irradiation portion) so as not to penetrate the hydrophobic portion (ultraviolet ray irradiation portion) to form a patterned source and drain electrode. Although the coating method of an image forming liquid is not specifically limited, such as a spin coat method and the casting method, The inkjet printing method and the spray coating method which are easy to control liquid quantity are preferable.

Finally, organic semiconductor materials such as pentacene and polythiophene, which are active layers of the organic FET, are formed. The method of forming the organic semiconductor material is not particularly limited, but for example, a vacuum coating method or a spin coating method, a casting method, an inkjet printing method or a spray coating method may be used.

In the organic FET fabricated as described above, the manufacturing process can be greatly reduced, and since the organic FET having a channel shorter than the mask deposition method can be manufactured, a large current can be extracted even when a low mobility organic semiconductor material is used as the active layer. . In addition, since the underlayer film for forming an image obtained by the method of the present invention has excellent electrical insulating property, it can also be used as a gate insulating layer, and the manufacturing process can be further simplified.

Example

Although an Example is given to the following and this invention is demonstrated to it in more detail, this invention is not limited to this.

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

The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) of the polyimide precursors obtained according to the following Synthesis Examples were determined by the following apparatus and measurement conditions by GPC (at room temperature gel permeation chromatography). It measured and calculated by the polyethyleneglycol (or polyethylene oxide) conversion value.

GPC device: Shodex (registered trademark) (GPC-101) made by Showa Denko K.K.

Column: Shodex (registered trademark) made by Showa Denko K.K. (serial of KD803, KD805)

Column Temperature: 50 ℃

Eluent: N, N-dimethylformamide

(As an additive, 30 mmol / L of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / L of phosphoric acid anhydride (o-phosphate), 10 ml / L of tetrahydrofuran (THF))

Flow rate: 1.0ml / min

Standard sample for calibration curve preparation:

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

Polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) made by Polymer Laboratories Ltd.

[Measurement of film thickness]

The film thickness of the polyimide membrane was stripped of a portion of the membrane with a caterpillar knife, and the step was measured using a fully automatic micrometer (ET4000A, manufactured by Kosaka Laboratory Ltd.) with a measuring force of 10 μN and a sweep speed of 0.05 mm / sec. It measured and calculated | required.

[Investigation of ultraviolet rays]

Ultraviolet rays were irradiated onto the polyimide film through a band pass filter through which a high-pressure mercury lamp passed light having a wavelength of 254 nm as a light source.

In calculating the exposure amount on the polyimide film, the illuminance of the ultraviolet ray was measured by attaching a probe for Deep UV having a peak sensitivity at a wavelength of 253.7 nm to an illuminometer (MODEL306, manufactured by OAI Corporation).

The obtained roughness was 45-50 mW / cm <2>. The obtained illuminance was multiplied by the exposure time to obtain an exposure amount (J / cm 2).

[Measurement of Contact Angle]

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

The contact angle of water was measured after stopping 3 microliters of liquid quantity and 5 second after liquid landing.

The contact angle of propylene glycol monomethyl ether (PGME) was measured after stopping for 5 second after liquid quantity 3.0-3.5 microliters and liquid.

Synthesis Example

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

Under nitrogen atmosphere, a tetrahydrofuran (155 g) solution of compound [ii] (20.00 g, 69.79 mmol) and triethylamine (8.07 g, 79.76 mmol) was cooled to 10 ° C. or lower, and compound [i] (15.33 g, 66.47 A tetrahydrofuran (70 g) solution of mmol) was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was increased to 23 ° C., and the reaction was further performed. After completion of the reaction by HPLC (high-performance liquid chromatography), the reaction solution was poured into distilled water (1.8 L), and the precipitated solid was filtered, washed with water, and washed with methanol (192 g) to obtain compound [iii] (amount of 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 (2H, t), 1.73-1.67 (2H, m), 1.48-1.37 (2H, m), 1.23 (28H, s), 0.86 (3H, t).

Under a nitrogen atmosphere, a mixture of 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., followed by ammonium chloride (6.66 g, 124.5). 10% aqueous solution of mmol) was added dropwise. After completion of the reaction by HPLC, the solid was filtered by celite filtration. After washing with ethyl acetate and 200 mL each of distilled water, the aqueous layer was removed and the organic layer was washed three times with distilled water (300 mL). Thereafter, the organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off. The crude product of the obtained compound (DA-1) was recrystallized from methanol (104 g) to obtain compound (DA-1) (yield amount: 11.7 g, yield: 67%).

¹ H-NMR (400 MHz, 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 Polyimide Precursor (PI-1)

1.2621 g (0.003 mol) of 3,5-diaminothiobenzoate octadecyl (DA-1) prepared in Synthesis Example 1 was added to a 50 mL four-necked flask under nitrogen stream, followed by N-methyl-2-pyrrolidone (hereinafter NMP) was dissolved in 10.42g, and then 0.5766g (0.003mol) of 1,2,3,4-cyclobutanetetracarboxylic anhydride (hereinafter CBDA) was added and stirred at 23 ° C for 10 hours to carry out the polymerization reaction and further By diluting with NMP, 8 mass% solution of the polyimide precursor (PI-1) was obtained.

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

Synthesis Example 3 Synthesis of Polyimide Precursor (PI-2)

In a 50 mL four-necked flask under nitrogen stream, DA-1 0.8835 g (0.0021 mol) and p-phenylenediamine (p-PDA) 0.0973 g (0.0009 mol) were added and dissolved in NMP 8.83 g, followed by CBDA 0.5766. 6 mass% solution of the polyimide precursor (PI-2) was obtained by adding g (0.00294 mol) and stirring this at 23 degreeC for 10 hours, superposing | polymerizing and diluting with NMP further.

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

Synthesis Example 4 Synthesis of Polyimide Precursor (PI-3) of Comparative Example

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

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

Synthesis Example 5: Diamine Compound (DA-2)

Synthesis of DA-2

Under nitrogen atmosphere, compound [iv] (42.63 g, 209.9 mmol), compound [v] (102.97 g, 230.9 mmol), copper powder (29.35 g, 461.8 mmol), 2,2'-bipyridyl (3.28 g, 20.99 mmol) and dimethyl sulfoxide (341 g) were stirred at 120 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was added to distilled water (2730 g) and filtered, and the filtrate was washed with distilled water (2 L) and ethyl acetate (1.5 L). 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. Then, the compound [vi] was obtained by filtration and solvent distillation (amount of yield: 75.33g, yield: 81%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.48 (2H, d), 7.32 (2H, d), 2.52 (3H, s).

In an acetonitrile (347 g) / pure (17 g) solution of compound [vi] (52.00 g, 117.6 mmol) under a nitrogen atmosphere, N-fluoro-N '-(chloromethyl) triethylenediaminebis (tetrafluoroborate) (43.63 g, 123.2 mmol) was added and the reaction was carried out at 23 ° C. After confirming completion of reaction by HPLC, the solvent was distilled off. Dichloromethane (1.2L) was added, and saturated sodium bicarbonate water (700 mL) was added little by little. After the aqueous layer was removed, the organic layer was washed three times with saturated brine (700 mL) and the organic layer was dried over anhydrous magnesium sulfate. Thereafter, filtration and solvent removal were performed to obtain compound [vii] (amount of 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).

Under nitrogen atmosphere, acetic anhydride (46.39 g, 454.4 mmol) was added to compound [vii] (26.03 g, 56.8 mmol), and the reaction was carried out under reflux. After 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 obtain compound [viii] (amount: 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, an aqueous 28% ammonia solution (13.73 g) was added to a methanol (150 g) solution of compound [viii] (37.67 g, 75.3 mmol), followed by stirring at 23 ° C. After completion of the reaction by HPLC, the pH was adjusted to 6 with 35% hydrochloric acid and the solvent was distilled off. Thereafter, the crude product was dissolved in dichloromethane (1 L), washed three times with saturated brine (500 mL), and dried over anhydrous magnesium sulfate. Then, the mixture was filtered and the solvent was distilled off to obtain compound [ix] (amount of 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).

Under a nitrogen atmosphere, a tetrahydrofuran (139 g) solution of compound [ix] (31.00 g, 72.4 mmol) and triethylamine (7.33 g, 72.4 mmol) was cooled to 10 DEG C or lower, and compound [i] (15.90 g, 68.95 mmol) of tetrahydrofuran (100 g) solution was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further performed. After completion of the reaction by HPLC, the reaction solution was added to distilled water (1.9 L), and the precipitated solid was filtered and washed with water and then recrystallized with 2-propanol (257 g) to obtain Compound [x] (yield: 27.01 g, yield: 63%).

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

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

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.75 (4H, s), 6.73 (2H, d), 6.44 (1H, t), 3.76 (4H, brs).

Synthesis Example 6 Diamine Compound (DA-3)

Synthesis of DA-3

Under nitrogen atmosphere, compound [iv] (27.05 g, 133.2 mmol), compound [xi] (80.00 g, 146.5 mmol), copper powder (18.62 g, 293.0 mmol), 2,2'-bipyridyl (2.08 g, 13.32 mmol) and dimethyl sulfoxide (216 g) were stirred at 120 ° C. After confirming the completion of the reaction by HPLC, the reaction solution was added to distilled water (1730 g) and filtered, and the filtrate was washed with distilled water (1 L) and ethyl acetate (1 L). 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. Then, the compound [xii] was obtained by filtering and distilling a solvent (yield amount: 65.72g, yield: 91%).

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

In an acetonitrile (333 g) / pure (17 g) solution of compound [xii] (50.00 g, 92.21 mmol) under a nitrogen atmosphere, N-fluoro-N '-(chloromethyl) triethylenediaminebis (tetrafluoroborate) (32.67 g, 92.21 mmol) was added and the reaction was carried out at 23 ° C. After confirming completion of reaction by HPLC, the solvent was distilled off. Dichloromethane (800 mL) was added and saturated sodium bicarbonate water (500 mL) was added little by little. After the aqueous layer was removed, the organic layer was washed three times with saturated brine (500 mL), and the organic layer was dried over anhydrous magnesium sulfate. Thereafter, filtration and solvent removal were performed to obtain compound [xiii] (amount of 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).

Under nitrogen atmosphere, trifluoroacetic anhydride (220.56 g, 1.05 mol) was added to compound [xiii] (70.63 g, 126.5 mmol), and the reaction was carried out under reflux. After completion of the reaction by HPLC, the solvent was distilled off to obtain a crude product. And methanol (226g) and triethylamine (211.89g) were added, after stirring at 23 degreeC for 30 minutes, solvent removal was performed. The obtained crude product was dissolved in ethyl acetate (1L), washed twice with saturated aqueous ammonium chloride solution (1L) and saturated brine (1L), and then the organic layer was dried over magnesium sulfate and the solvent was distilled off to obtain a compound [xiv]. (Yield: 64.7g, Yield: 97%).

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

Under nitrogen atmosphere, a tetrahydrofuran (290 g) solution of compound [xiv] (69.00 g, 130.62 mmol) and triethylamine (13.22 g, 130.62 mmol) was cooled to 10 ° C. or lower, and compound [i] (28.68 g, 124.40 A tetrahydrofuran (145 g) solution of mmol) was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further performed. After completion of the reaction by HPLC, the reaction solution was added to distilled water (3.5 L), and the precipitated solid was filtered and washed with water and then recrystallized with 2-propanol (270 g) to obtain a compound [xv] (amount: 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).

Under nitrogen atmosphere, a mixture of compound [xvii] (8.00 g, 11.1 mmol), 3% platinum carbon (0.3% iron support, hydrate, 1.6 g, 20 wt%) and methanol (120 g) was stirred at 23 ° C. in the presence of hydrogen. did. After confirming the completion of the reaction by HPLC, the reaction mixture was filtered through Celite, and the Celite was washed with methanol (30 mL) to remove the solvent. The crude product of the obtained compound (DA-3) was dispersed and washed with 2-propanol (28 g), filtered and dried to obtain the compound (DA-3) (amount of yield: 5.6 g, yield: 76%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 7.75 (4H, s), 6.73 (2H, d), 6.44 (1H, t), 3.76 (4H, brs).

Synthesis Example 7: Diamine Compound (DA-4)

Synthesis of DA-4

Under nitrogen atmosphere, a tetrahydrofuran (90 g) solution of compound [xvi] (21.87 g, 45.54 mmol) and triethylamine (4.61 g, 45.54 mmol) was cooled to 10 DEG C or lower, and compound [i] (10.00 g, 43.37 A tetrahydrofuran (60 g) solution of mmol) was added dropwise while paying attention to exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and the reaction was further performed. After completion of the reaction by HPLC (high-performance liquid chromatography), the reaction solution was added to distilled water (1.2 L), and the precipitated solid was filtered, washed with water, and washed with 2-propanol (232 g) to give 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).

Under nitrogen atmosphere, a mixture of 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., followed by ammonium chloride (5.95 g, 111.3). 10% aqueous solution of mmol) was added dropwise. After completion of the reaction by HPLC, the solid was filtered by celite filtration. After washing with ethyl acetate and 500 mL each of distilled water, the aqueous layer was removed and the organic layer was washed three times with distilled water (500 mL). Thereafter, the organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off. The crude product of the obtained compound (DA-4) was dispersed and washed with hexane (60 g), filtered and dried to obtain the compound (DA-4) (amount of yield: 19.5 g, yield: 85%).

¹ H-NMR (400 MHz, DMSO-d ₆ , δ ppm): 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 Polyimide (PI-4)

Under nitrogen stream, 3.5837 g (8.73 mmol) of 2,2-bis (4-aminophenoxyphenyl) propane (hereafter BAPP) and DA-2 0.1518 g (0.27 mmol) were added to a 100 mL four-necked flask and NMP 36.02 g. After dissolving in, 2.6214 g (8.73 mmol) of 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene dianhydride (hereinafter TDA) was added and stirred at 50 ° C. for 24 hours. The polymerization reaction was carried out. The solution of the obtained polyamic acid was diluted to 8 mass% with NMP.

To 30 g of the solution, 11 g of acetic anhydride and 5.2 g of pyridine were added as an imidization catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimide solution. The white precipitate obtained by throwing the solution in a large amount of methanol was filtered and dried to obtain a white polyimide powder. It was confirmed that the polyimide powder was imidized at 90% or more than 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 polyimide (PI-4).

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

Synthesis Example 9: Synthesis of Polyimide (PI-5)

Under nitrogen stream, 3.4728 g (8.46 mmol) of BAPP and 0.3037 g (0.54 mmol) of DA-2 were dissolved in a 100 mL four-necked flask, dissolved in 36.25 g of NMP, and then 2.6214 g (8.73 mmol) of TDA was added thereto. The mixture was stirred for 24 hours to carry out the polymerization reaction. The solution of the obtained polyamic acid was diluted to 8 mass% with NMP.

To 30 g of the solution, 11 g of acetic anhydride and 5.2 g of pyridine were added as an imidization catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimide solution. The solution was poured into a large amount of methanol, and the white precipitate obtained was filtered and dried to obtain a white polyimide powder. It was confirmed that the polyimide powder was imidized at 90% or more than ¹ H-NMR. 2.1 g of the 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 polyimide (PI-5).

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the obtained polyimide (PI-5) were Mn = 16,400 and Mw = 39,400, respectively.

Synthesis Example 10 Synthesis of Polyimide (PI-6)

Under nitrogen stream, 3.6206 g (8.82 mmol) of BAPP and 0.1192 g (0.18 mmol) of DA-3 were added to a 100 mL four-necked flask, dissolved in 36.05 g of NMP, and then 2.6214 g (8.73 mmol) of TDA was added thereto. It stirred at 24 degreeC for 24 hours and superposed | polymerized reaction. The solution of the obtained polyamic acid was diluted to 8 mass% with NMP.

To 30 g of the solution, 11 g of acetic anhydride and 5.2 g of pyridine were added as an imidization catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimide solution. The white precipitate obtained by throwing the solution in a large amount of methanol was filtered and dried to obtain a white polyimide powder. It was confirmed that the polyimide powder was imidized at 90% or more than ¹ H-NMR. 2.1 g of the 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 polyimide (PI-6).

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

Synthesis Example 11: Synthesis of Polyimide (PI-7)

Under nitrogen stream, BAPP 3.9819g (9.7mmol) and DA-4 0.1842g (0.3mmol) were dissolved in NMP 40.11g in a 100mL four-necked flask, followed by adding 2.9126g (9.7mmol) of TDA to 50 It stirred at 24 degreeC for 24 hours and superposed | polymerized reaction. The solution of the obtained polyamic acid was diluted to 8 mass% with NMP.

To 30 g of the solution, 11 g of acetic anhydride and 5.2 g of pyridine were added as an imidization catalyst, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimide solution. The white precipitate obtained by throwing the solution in a large amount of methanol was filtered and dried to obtain a white polyimide powder. It was confirmed that the polyimide powder was imidized at 90% or more than ¹ H-NMR. 2.1 g of the 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% by mass solution of polyimide (PI-7).

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

Synthesis Example 12 Synthesis of Polyimide Precursor (PI-8)

Under nitrogen stream, BAPP 3.9819g (9.7mmol) and DA-40.1842g (0.3mmol) were dissolved in NMP 34.39g in a 100mL four-necked flask, followed by the addition of 1.9023g (9.7mmol) of CBDA and 23 ° C. After stirring for 10 hours to carry out the polymerization reaction and further diluted with NMP, a 6% by mass solution of polyimide precursor (PI-8) was obtained.

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

Synthesis Example 13 Synthesis of Polyimide (PI-9) for Blend

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

To 50 g of the solution, 10.8 g of acetic anhydride and 5.0 g of pyridine were added as an imidization catalyst, and reacted at 50 ° C for 3 hours to obtain a polyimide solution. The white precipitate obtained by throwing the solution in a large amount of methanol was filtered and dried to obtain a white polyimide powder. It was confirmed that the polyimide powder was imidized at 90% or more than ¹ H-NMR. 4 g of the 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 polyimide (PI-9).

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

Synthesis Example 14 Preparation of Polymer Blend (Composition A)

9 g of 6 wt% solution of polyimide (PI-9) prepared in Synthesis Example 13 and 1 g of 6 wt% solution of polyimide (PI-7) prepared in Synthesis Example 11 were mixed and stirred at room temperature for 6 hours to obtain Composition A.

Synthesis Example 15 Preparation of Polymer Blend (Composition B)

9 g of a 6 wt% solution of polyimide (PI-9) prepared in Synthesis Example 13 and 1 g of a 6 wt% solution of polyimide (PI-8) prepared in Synthesis Example 12 were mixed and stirred at room temperature for 6 hours to obtain Composition B.

Synthesis Example 16 Preparation of Polymer Blend (Composition C)

8 g of a 6 wt% solution of polyimide (PI-9) prepared in Synthesis Example 13 and 2 g of a 6 wt% solution of polyimide (PI-8) prepared in Synthesis Example 12 were mixed and stirred at room temperature for 6 hours to obtain Composition C.

The structural formulas of the tetracarboxylic anhydride and the diamine compound synthesized or used in the present examples are shown below.

[Tetracarboxylic dianhydride used in this Example]

[Diamine Used in This Example]

Example 1 Water Contact Angle Change

The PI-1 solution prepared in Synthesis Example 2 was added dropwise to a glass substrate with ITO (2.5 cm in length and 0.7 mm in thickness) using a syringe with a 0.2 μm pore filter and applied by spin coating. Thereafter, the mixture was heated for 5 minutes under a hot plate at 80 ° C. to volatilize the organic solvent, and then calcined for 30 minutes on a 210 ° C. hot plate to obtain a polyimide film having a film thickness of about 400 nm. The water contact angle θ (°) of the polyimide membrane was measured.

Two polyimide membranes were produced by the same method, and the ultraviolet rays were irradiated at an irradiation dose of 20 J / cm 2 or 40 J / cm 2, and then the water contact angle θ (°) of the membrane was measured.

The results are shown in Table A.

Example 2 Hand Contact Angle Change

Except for using the solution of PI-2 prepared in Synthesis Example 3, three polyimide membranes were prepared in the same manner as in Example 1, and irradiated with ultraviolet-unirradiated film, ultraviolet-ray 20J / cm 2 or ultraviolet-ray 40J / cm 2, respectively. Each water contact angle θ (°) was measured as a film.

The results are shown in Table A.

<Comparative Example 1> Change of water contact angle

Except for using the PI-3 solution prepared in Synthesis Example 4, two polyimide membranes were prepared in the same manner as in Example 1, and the water contact angle θ (°) was measured using a non-ultraviolet irradiated membrane or a membrane irradiated with ultraviolet rays 40 J / cm 2, respectively. did.

The results are shown in Table A.

Example 3 PGME Contact Angle Change

Three polyimide membranes were prepared in the same manner as in Example 1, and the contact angle θ (°) of the PGME was measured using a non-irradiated film, a film irradiated with ultraviolet light 2J / cm 2, or a film irradiated with ultraviolet light 6J / cm 2, respectively.

The results are shown in Table B.

Comparative Example 2 PGME Contact Angle Change

Except for using the PI-3 solution prepared in Synthesis Example 4, two polyimide membranes were prepared in the same manner as in Example 1, and the contact angle θ (°) of the PGME was used as a non-irradiated membrane or a membrane irradiated with ultraviolet rays 6J / cm 2, respectively. ) Was measured.

The results are shown in Table B.

Example 4 PGME Contact Angle Change

A solution of PI-4 prepared in Synthesis Example 8 was added dropwise to a glass substrate with ITO (2.5 cm wide and 0.7 mm thick) in a syringe with a 0.2 μm pore filter and applied by spin coating. Thereafter, the mixture was heated for 5 minutes with an 80 ° C. hot plate to volatilize the organic solvent, and baked for 30 minutes with a 180 ° C. hot plate to obtain a polyimide film having a film thickness of about 400 nm. The contact angle of the PGME solution of this polyimide membrane was measured.

One polyimide membrane was produced by the same method, and the ultraviolet-ray was irradiated with the irradiation amount of 1J / cm <2>, and the contact angle (theta) (degree) of PGME was measured.

The results are shown in Table C.

Example 5 PGME Contact Angle Change

Except for using PI-5 prepared in Synthesis Example 9, two polyimide films were prepared in the same manner as in Example 4, and the contact angle θ (°) of the PGME was measured using a non-ultraviolet irradiated film and a UV irradiated film of 1J / cm 2, respectively. did.

The results are shown in Table C.

Example 6 PGME Contact Angle Change

Except for using PI-6 prepared in Synthesis Example 10, two polyimide films were prepared in the same manner as in Example 4, and the contact angle θ (°) of the PGME was measured using a film irradiated with an ultraviolet non-irradiated film and ultraviolet light 1J / cm 2, respectively. did.

The results are shown in Table C.

Example 7 PGME Contact Angle Change

Except using the composition A prepared in the synthesis example 14, two polyimide membranes were produced by the same method as Example 4, and the contact angle (theta) (degree) of PGME was measured using the film which irradiated the ultraviolet unilluminated membrane and the ultraviolet-ray 1J / cm <2>, respectively. .

The results are shown in Table C.

Example 8 PGME Contact Angle Change

Except using the composition C prepared in the synthesis example 16, two polyimide membranes were produced by the same method as Example 6, and the contact angle (theta) (degree) of PGME was measured using the film which irradiated the ultraviolet unilluminated membrane and the ultraviolet-ray 1J / cm <2>, respectively. .

The results are shown in Table C.

As shown in Tables A, B and C, in the examples using polyimide and polyimide precursors made of diamines having thiol bonds in the side chains, the contact angle of PGME after ultraviolet irradiation was greatly changed in all cases.

On the other hand, in Comparative Examples 1 and 2 using the polyimide precursor (PI-3) produced without using a diamine having a thiol bond in the side chain, the amount of change in the contact angle of water or PGME was small.

The result is that the side chain of the polyimide precursor has a structure in which a hydrophobic group exists through a thiol ester group, that is, the thiol ester group is photolyzed by ultraviolet irradiation, and the hydrophobic portion of the side chain is cleaved and separated from the main chain, thereby greatly changing the hydrophilicity. It is thought that it led to the result.

Example 9 Evaluation of Electrode Patterning Properties

A solution of PI-4 prepared in Synthesis Example 8 was added dropwise to a glass substrate with ITO (2.5 cm wide and 0.7 mm thick) with a syringe with a 0.2 μm pore filter and applied by spin coating. Thereafter, the mixture was heated for 5 minutes with a hot plate at 80 ° C. in an atmosphere, followed by volatilization of an organic solvent, and baking for 30 minutes with a hot plate at 180 ° C. to obtain a polyimide film having a film thickness of about 400 nm. Ultraviolet 1J / cm <2> was irradiated to the said polyimide film through the photomask (line-and-space of a line width of 100 micrometers, and a pitch of 100 micrometers), and a part of polyimide was hydrophilized. The silver fine particle dispersion was dropped in a small amount onto an ultraviolet irradiation section and fired for 60 minutes on a 180 ° C. hot plate to form a silver electrode having a thickness of 50 nm.

The micrograph of the said silver electrode is shown in FIG. The film made of PI-4 was able to form a silver electrode of desired line width.

Example 10 Evaluation of Electrode Patterning Properties

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, and ultraviolet light 1J / cm 2 was applied to the polyimide film through a photomask (line and space having a line width of 100 µm and a pitch of 100 µm). It investigated and hydrolyzed a part of polyimide. The silver fine particle dispersion was dropped in a small amount onto the ultraviolet irradiation section and fired for 60 minutes on a 180 ° C. hot plate to form a silver electrode having a thickness of 50 nm.

The micrograph of this silver electrode is shown in FIG. The film made of the composition A was able to form a silver electrode having a desired line width.

Comparative Example 3 Evaluation of Electrode Patterning Properties

A polyimide film was formed in the same manner as in Example 11 except that the firing temperature was set to 210 ° C. using PI-3 prepared in Synthesis Example 4, and a photomask (line width of 100 μm in line width and 100 μm in pitch) was formed on the polyimide film. 1J / cm 2 of ultraviolet rays were irradiated through the space). Thereafter, a small amount of the silver fine particle dispersion was dropped, but the electrode could not be formed because the ultraviolet irradiation part was not hydrophilized.

In Example 9, the results of Example 10 and Comparative Example 3 are shown in Table D.

The film composed of PI-4 having a thiol ester bond and the composition A was sufficiently hydrophilic at 1J / cm 2 UV irradiation amount and could form a silver electrode having a 100 μm line width, but the film made of the composition D having no thiol ester bond The amount of ultraviolet irradiation of 1 J / cm 2 did not change sufficiently to be hydrophilic, and thus electrode formation was impossible.

Example 11 Insulation

A solution of PI-1 prepared in Synthesis Example 2 was added dropwise to a glass substrate with ITO (2.5 cm wide and 0.7 mm thick) using a syringe with a 0.2 μm pore filter and applied by spin coating. Thereafter, the mixture was heated for 5 minutes with an 80 ° C. hot plate to volatilize the organic solvent, and calcined for 30 minutes with a 210 ° C. hot plate to obtain a polyimide film having a thickness of about 450 nm.

In order to obtain good contact between the ITO electrode and the probe of the measuring device, a part of the polyimide film was removed to expose the ITO, and then a vacuum deposition device was used to expose aluminum having a diameter of 1.0 mm and a film thickness of 100 nm on the polyimide film and the ITO. The electrodes were stacked. At this time, vacuum deposition conditions were made into room temperature, the vacuum degree 3 * 10 <^-3> Pa or less, and aluminum deposition rate 0.3nm / sec or less. The electrode for the current-voltage characteristic evaluation of a polyimide membrane was produced by forming an electrode above and below a polyimide membrane by such a method.

The fabricated sample immediately measured the current-voltage characteristics in a nitrogen atmosphere. The measurement voltage was every 2V from 0V to 90V. At this time, the dielectric constant of the polyimide film was 3.37 and the leak current density was 3 × 10 ^-10 A / cm 2. The polyimide film was not subjected to dielectric breakdown at an electric field of 2 MV / cm.

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

Next, after leaving the same sample as above for 15 hours in air | atmosphere (25 degree | times, 45% of humidity), the current-voltage characteristic was measured. The measurement voltage was set at every 2V from 0V to 90V. At this time, the leakage current density of the sample was 1.8 × 10 ^-7 A / cm 2.

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

Example 12 Insulation

A sample for current-voltage characteristics was produced in the same manner as in Example 11 except that the firing temperature of the polyimide film was 230 ° C. At this time, the dielectric constant of the polyimide film was 3.14 and the leak current density was 1.0 × 10 ^-10 A / cm 2. In addition, the polyimide film was not destroyed in an electric field of 2 MV / cm.

And the same sample as above was left to stand in air | atmosphere (25 degree | times, humidity of 45%) for 15 hours, and the current-voltage characteristic was measured. The measurement voltage was set at every 2V from 0V to 90V. At this time, the leakage current density of the sample was 1.8 × 10 ^-8 A / cm 2.

The measurement result in nitrogen atmosphere is shown in FIG. 3, and the measurement result of the current-voltage characteristic of air | atmosphere is shown in FIG.

Example 13 Insulation

A solution of PI-4 prepared in Synthesis Example 8 was added dropwise to a glass substrate with ITO (2.5 cm wide and 0.7 mm thick) in a syringe with a 0.2 μm pore filter and applied by spin coating. Then, the organic solvent was volatilized for 5 minutes on 80 degreeC hotplate in air | atmosphere, and it baked for 30 minutes on the 180 degreeC hotplate, and obtained the polyimide film of about 400 nm in thickness. In order to obtain good contact between the ITO electrode and the probe of the measuring device, a part of the polyimide film was removed to expose the ITO, and then a vacuum deposition device was used to expose aluminum having a diameter of 1.0 mm and a film thickness of 100 nm on the polyimide film and the ITO. The electrodes were stacked. At this time, vacuum deposition conditions were made into room temperature, the vacuum degree 3 * 10 <^-3> Pa or less, and aluminum deposition rate 0.3nm / sec or less. By forming electrodes above and below the polyimide film in this manner, a sample for current-voltage characteristic evaluation of the polyimide film was produced.

The samples were allowed to stand for 5 hours in an environment of 23 ° C ± 3 ° C and 45% ± 5% of temperature, and then the current voltage characteristics were measured. The measured voltage was set at every 2V from 0V to 100V. The leak current density at 1 MV / cm of this sample was 4.3 × 10 ^-11 A / cm 2. In addition, the polyimide film was not destroyed by 2 MV / cm.

5 shows measurement results of current-voltage characteristics.

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 leak current density at 1 MV / cm of this sample was 1.7 × 10 ^-10 A / cm 2. In addition, the polyimide film was not destroyed by 2 MV / cm.

5 shows measurement results of current-voltage characteristics.

Example 15 Insulation

Using the composition B prepared in Synthesis Example 15, a sample for current-voltage evaluation was produced in the same manner as in Example 13 except that the firing temperature was 230 ° C.

The leakage current density at 1 MV / cm of this sample was 1.2 x 10 ^-10 A / cm 2, and the polyimide film was not subjected to dielectric breakdown until 2 MV / cm.

5 shows measurement results of current-voltage characteristics.

Example 16 Insulation

Using the composition C prepared in Synthesis Example 16, a sample for current-voltage evaluation was produced in the same manner as in Example 13 except that the firing temperature was set to 230 ° C.

The leak current density at 1 MV / cm of this sample was 3.4 × 10 ^-10 A / cm 2. In addition, the polyimide film was not destroyed by 2 MV / cm.

5 shows measurement results of current-voltage characteristics.

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

In addition, as shown in FIG. 4, the film made of PI-1 showed an increase in the leakage current density in the air, which is susceptible to moisture, compared to that in the nitrogen atmosphere. However, there is no problem in the use as an underlayer film for image formation. (Example 11 and Example 12).

As shown in Fig. 5, the films made of PI-4 and the compositions A to C were all excellent insulating films (Examples 13 to 16).

That is, the underlayer film for image formation of the present invention was an underlayer film having sufficient insulation performance as the underlayer film for image formation.

Example 17 Transistor Characteristics

A solution of PI-4 prepared in Synthesis Example 8 was added dropwise to a glass substrate with a Cr electrode (2.5 cm wide and 0.7 mm thick) in a syringe with a 0.2 μm pore filter and applied by spin coating. Thereafter, the mixture was heated for 5 minutes under an air hot plate at 80 ° C. to volatilize the organic solvent, and calcined for 30 minutes with a hot plate at 180 ° C. to obtain a polyimide film having a film thickness of about 450 nm. Ultraviolet 2J / cm <2> was irradiated to this polyimide membrane through the photomask, and a part of polyimide was hydrophilized. The silver fine particle dispersion was appropriately added dropwise to the ultraviolet irradiation section and fired for 60 minutes on a 180 ° C. hot plate to form a source / drain electrode having a film thickness of 50 nm.

A pentacene (aldrich) film was formed at 70 nm on the silver electrode by vacuum deposition. The deposition rate of pentacene was 0.05 nm / sec.

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

Specifically, the source / drain voltage (V _D ) is -80V, the gate voltage (V _G ) is changed from + 20V to -80V in 2V steps, and the voltage is maintained for 1 second until the current is sufficiently stabilized at each voltage. The value after holding was recorded as the measured value of drain current, and the said operation was repeated 5 times. In addition, it measured in the nitrogen atmosphere using the semiconductor parameter analyzer HP4156C (made by Agilent Technologies).

In general, the drain current I _D at saturation It can be represented by the following formula. That is, the mobility μ of the organic semiconductor can be obtained from the slope of the graph when the square root of the absolute value of the drain current I _D is plotted on the vertical axis and the gate voltage V _g is plotted on the horizontal axis.

I _D = WCμ (V _G -V _T ) ² / 2L

Where W is the channel width of the transistor, L is the channel length of the transistor, c is the capacitance of the gate insulating film, and V _T is The threshold voltage of the transistor, μ, is the mobility. The transistors fabricated in this example were W = 2 mm, L = 100 m, and C = 6.4 nF / cm 2.

The mobility (pent) of pentacene was calculated based on this formula, and the average was 5 * 10 <^-2> cm <2> / Vs. The threshold voltage was -18 to -20V, and the ratio (on / off ratio) between the on state and the off state was 10 ⁶ . In addition, even when repeated measurements were carried out, no shift in transfer characteristics was found and stable characteristics were obtained (Fig. 6).

It was shown that the film obtained in PI-4 was excellent not only as an electrode forming film but also as a gate insulating film for organic transistors.

Example 18 Transistor 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 transistors fabricated in this example were W = 2 mm, L = 100 m, and C = 6.5 nF / cm 2.

The mobility of pentacene (μ) was calculated based on this equation, and the average value was 5x10 ^-2 cm 2 / Vs. The threshold voltage was -19 to -21V, and the ratio between on and off states (on / off). Off ratio) was 10 ⁶ . Further, even when repeated measurement was performed, no shift in the transfer characteristic was found and stable characteristics were obtained (Fig. 7).

It was shown that the film obtained in the composition A was excellent not only as an electrode forming film but also as a gate insulating film for organic transistors.

Example 19 Transistor Characteristics

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

The mobility μ of pentacene was calculated based on this equation, and the average was 3 × 10 ⁻² cm 2 / Vs. The threshold voltage was -16 to -20V, and the ratio (on / off ratio) between the on state and the off state was 10 ⁶ . In addition, even when repeated measurement was performed, no shift of the transfer characteristic was found and stable characteristics were obtained (FIG. 8).

It was shown that the film obtained in the composition A was excellent not only as an electrode forming film but also as a gate insulating film for organic transistors.

The underlayer film for forming an image according to the present invention can realize a shortening of the required exposure time for changing the hydrophilicity, and can reduce the manufacturing cost in forming a patterning layer of functional material such as an electrode.

Moreover, it is also possible to give anisotropy to the film | membrane obtained from the above-mentioned polyimide precursor and polyimide by irradiating polarized UV. That is, it can be used also as an orientation treatment film of functional materials, such as a liquid crystal and a semiconductor, and can shorten manufacturing time like the case where it used for the base film for image formation.

Claims (14)

An underlayer film for forming an image, comprising a polyimide precursor having a repeating structure represented by the following formula (1) or a polyimide obtained by dehydrating the polyimide precursor.
[Formula 1]

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

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 with a fluorine atom, and each 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).
Dehydration of the polyimide precursor or the polyimide precursor obtained by reacting a tetracarboxylic dianhydride component comprising a tetracarboxylic dianhydride represented by the following formula (6) and a diamine component comprising a diamine represented by the formula (7) An underlayer film for image formation, comprising a polyimide obtained by ring closure.
(3)

[Wherein, A represents a tetravalent organic group, and B represents formula (2) or formula (3)
[Chemical Formula 4]

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 with a fluorine atom, and each 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).
3. The method according to claim 1 or 2,
An underlayer film for image formation, wherein Z in Formula (2) or (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms in which any hydrogen atom is substituted with a fluorine atom.
4. The method according to any one of claims 1 to 3,
The lower layer film for image formation which has a tetravalent organic group which A has an aliphatic ring or consists only of aliphatic.
The method according to any one of claims 1 to 4,
An underlayer film for image formation, wherein B represents a divalent structure represented by Formula (2).
The method according to any one of claims 1 to 5,
An underlayer film for forming an image wherein X and Y exhibit a single bond.
An organic transistor having the image forming underlayer film according to any one of claims 1 to 6.
Diamine compound represented by following formula (14) or following formula (15).
[Chemical Formula 5]

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 in which any hydrogen atom is substituted with a fluorine atom, and each R independently represents a fluorine atom or 1 to 3 carbon atoms. An alkoxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3).
The polyimide precursor obtained by carrying out dehydration ring-closure of the polyimide precursor containing the repeating unit represented by following formula (1), or the said polyimide precursor.
[Formula 6]

(Wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2a) or formula (3a), and R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group). , n represents a natural number.)
[Formula 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 in which any hydrogen atom is substituted with a fluorine atom, and each R independently represents a fluorine atom or 1 to 3 carbon atoms. An alkoxy group or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3).
Dehydration of the polyimide precursor or the polyimide precursor obtained by reacting a tetracarboxylic dianhydride component comprising a tetracarboxylic dianhydride represented by the following formula (6) and a diamine component comprising a diamine represented by the formula (7) An image forming underlayer film coating liquid, comprising a polyimide obtained by ring closure.
[Chemical Formula 8]

(In formula, A represents a tetravalent organic group, B represents Formula (2) or Formula (3).
[Formula 9]

Represents a divalent structure represented by R ¹ , R ² each independently represents 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 is 3 to 26 carbon atoms which may be substituted with fluorine atoms An aliphatic hydrocarbon of R, independently R 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 image forming underlayer coating liquid according to claim 10, wherein Z in formula (2) or (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms in which any hydrogen atom is substituted with a fluorine atom.
12. The lower layer coating liquid for image forming according to claim 10 or 11, further comprising a soluble polyimide having an imidation ratio of 80% or more.
The image forming underlayer film obtained by baking the image forming underlayer film coating liquid of Claim 10-12.
An organic transistor having a film obtained by firing the image forming underlayer film coating liquid according to claim 10.

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