TW201031687A - Underlayer film for forming image - Google Patents

Abstract

An underlayer film for image formation, which is characterized by containing a polyimide precursor having a repeating structure represented by formula (1) or a polyimide obtained by dehydration ring closing of the polyimide precursor. In the formula, A represents a tetravalent organic group, and B represents a divalent organic group represented by formula (2) or (3).

Description

201031687 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an organic transistor produced by forming a lower layer film for an image and forming a film under the image. [Prior Art] At present, in the manufacturing steps of an electronic device, a masking method or a scribing method is mainly used for the pattern of the Φ film. These prior methods have been pointed out to have problems such as complex steps. In recent years, for these prior methods, the difference coating technique has been applied to the functional layer which is formed on the surface of the board to form a patterned layer composed of a field which is easily wetted by liquid, and then, A solution of the shape is applied to the patterned layer, and a functional film is formed on the dry φ wet field to produce a device or an organic FET (electric field effect transistor). The patterned layer for the functional film is known to contain a photo-contact with titanium oxide and an organic polyoxyalkylene (see, for example, Patent Document 1), a compound at a receiving portion, and a fluoropolymer. In the case where the mask is irradiated with ultraviolet light (for example, referring to the special purpose, it is also proposed to deposit a fluorine-based coating agent through the mask, and further to use a large-sized etching plate for forming an electrode or function photolithography. Difficulty and suggesting the use of a liquid wetting film in the patterning. The domain and the liquid are not easily wetted into a functional film material, only in the liquid emollient machine EL (electroluminescent device and other electronic devices have a transparent mask A method of irradiating a laser or a transparent article on a light-absorbing layer, such as a UV-ray dye, etc. 2), etc., and forming the above-described patterning layer-5-201031687 (for example, refer to Patent Document 3). The patterned layer proposed so far only fulfills the role of the patterning of the functional film, but remains in the component. Therefore, the patterned layer is durable to the subsequent steps and even in the electronic device. It is also necessary that the reliability of the characteristic is not adversely affected. The necessary characteristics of the patterned layer differ depending on the pattern used or the location of the patterned layer, wherein the patterning of the electrodes The electrical insulation of the layer is an important characteristic. ^ Also, the method proposed so far only focuses on the characteristics of the patterned layer. Therefore, for example, the source electrode and the drain electrode of the organic FET device are patterned. In addition, it is necessary to separately prepare a gate insulating film under the patterned layer. On the other hand, polyimine is excellent in heat resistance, mechanical strength, electrical insulating property, chemical resistance, etc., and has been used in various kinds of electrons. In the apparatus, the use of polyimine as a patterning layer has been disclosed using a tetracarboxylic anhydride having an alicyclic structure (for example, refer to Patent Document 4). However, in such cases, the amount of ultraviolet rays is extremely large. For this reason, it is necessary to carry out a long-term exposure process. Patent Document 1: JP-A-2000-223270 Patent Document 2: JP-A-2000-146478 Patent Document 3: Special Opening 2〇〇4·273 8 5 1 Bulletin patent document The present invention has been made in view of the above circumstances, and the present invention provides a method which can be easily changed even with a small amount of ultraviolet irradiation. The lower layer film for forming an image of the surface of the film on the surface of the underlayer film is formed. [The means for solving the problem] The present inventors have repeatedly reviewed the results of the above-mentioned objects and found that the polyimide precursor or The side chain of the polyimine obtained from the polyimine precursor contains a thiol ester structure, and can be exposed to a small amount on the surface of the cured film obtained from the polyimide precursor and the polyimide. The present invention has been completed in such a manner that the water contact angle becomes large, that is, the first aspect of the present invention relates to an underlayer film for forming an image, which is characterized by containing a polyimine precursor having a repetitive structure represented by the following formula (η) a polyphthalate obtained by dehydrating a ring of the polyimine precursor

R1OOC, /COOR2 -N - C - A - C - N - B I II II I Η Ο Ο Η

(wherein Α represents a tetravalent organic group, Β represents a divalent structure represented by the following formula (2) or (3), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group, and η represents a natural number); 201031687 [Chemical 2]

(2) Ο S-C-X-Y-2

(wherein 'X is not a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y is a single bond, -0-, -COO-, -oco-, -CONH-, _ch2o-, -ch2coo- or -ch2ch2coo-, Z indicates that it can be replaced by a fluorine atom

The aliphatic hydrocarbon group having 3 to 26 carbon 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 〇 to 3. A second aspect of the present invention relates to an underlayer film for forming an image,

The present invention is characterized in that it comprises a polyfluorene imine precursor obtained by reacting a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) with a diamine component containing a diamine represented by the formula (7). Or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: [Chemical 3] 0 〇

(6) H2N-B-NH2 (7) [wherein A represents a tetravalent organic group] B represents a divalent structure represented by the formula (2) or the formula (3): 201031687 [Chemical 4]

Z (R)t SCX—Υ—Ζ(R)t (wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, —0-, —COO—, - OCO-, -CONH-, -CH20-'-ch2coo- or -ch2ch2coo-, z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and each independently represents a fluorine atom and a carbon number of 1 to An alkoxy group of 3 or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 〇 to 3)]. The third aspect relates to the underlayer film for forming an image according to the first or second aspect, wherein Z of the formula (2) or the formula (3) represents an aliphatic group having 3 to 26 carbon atoms substituted by a fluorine atom of any hydrogen atom. Hydrocarbyl group. The fourth viewpoint is an underlayer film formed by the first to third aspects, wherein A represents a tetravalent organic group having an aliphatic ring or only an aliphatic group. The fifth aspect relates to an underlayer film for forming an image described in any one of the first to fourth aspects, wherein B represents a bivalent structure represented by the formula (2). The sixth aspect relates to the underlayer film for forming an image according to any one of the first to fifth aspects, wherein X and Y represent a single bond. The seventh aspect relates to an organic transistor characterized by comprising the image forming underlayer film according to any one of the first aspect to the sixth aspect. The eighth aspect relates to a diamine compound represented by the following formula (14) or the following formula (15) -9 - 201031687, [Chem. 5]

(wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -〇-, -COO-, -OCO-, -CONH-, -CH20-, -ch2coo - Or -CH2CH2COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted with a fluorine atom by any fluorine atom, and each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon number of 1 to An alkyl group of 3, t represents an integer of 0 to 3). The ninth aspect relates to a polyimine which contains a polyimine precursor of a repeating unit represented by the following formula (1) or which is obtained by dehydrating and ring-closing the polyimine precursor.

[Chemical 6]

R1OOC /COOR2

-NCACNB I II II I HO OH (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by the following formula (2a) or (3a), and R1 and R2 each independently represent a hydrogen atom or a monovalent organic group; , η represents a natural number); -10- 201031687 [Chem. 7]

(wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -0·, -COO-, -OCO-, -CONH-, -CH20_

, -ch2coo- or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or carbon. An alkyl group having 1 to 3 atoms, and t represents an integer of 0 to 3. The tenth aspect relates to a method for forming an image forming film of a lower layer, comprising a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and containing the formula (7). The polyimine precursor obtained by reacting the amine diamine component or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: [Chem. 8]

(6) H2N-B-NH2 (7) (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by formula (2) or formula (3): -11 - 201031687 [Chemical 9]

R1 and R2 each independently represent a hydrogen atom or a monovalent organic group 'X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -〇_, -COO-, -OCO-, - CONH-, -CH2〇·, -CH2COO- or

-CH2CH2COO_, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, t Represents an integer up to 3). The eleventh aspect is the lower layer film coating liquid for forming an image according to the tenth aspect, wherein the Z of the formula (2) or the formula (3) represents a fat having 3 to 26 carbon atoms in which any hydrogen atom is replaced by a fluorine atom. A hydrocarbon group.

The twelfth aspect is the image forming underlayer film coating liquid according to the tenth aspect or the eleventh aspect, which further comprises a soluble polyimine having a ruthenium iodide ratio of 80% or more. The thirteenth aspect relates to a layer film for forming an image, which is characterized in that the tenth aspect is the formation of the image forming underlayer film coating liquid described in the twelfth aspect. The fourteenth aspect relates to an organic transistor which is characterized by having a film obtained by firing the formed underlayer film coating liquid described in the tenth to thirteenth aspects. [Effect of the Invention] -12-201031687 The lower layer film for forming an image of the present invention has a small amount of ultraviolet irradiation amount, and the surface of the film is changed from hydrophobic to hydrophilic, whereby a functional material such as an electrode can be formed by using the characteristic. Waiting for the portrait. Therefore, the step time in the manufacture of the electronic device can be greatly shortened, and it becomes a material which is quite effective in terms of productivity. [Embodiment] The present invention relates to a novel formed image underlayer film containing a polyimine imine obtained from a polythioimine precursor having a thiol ester bond in a side chain or the polyimine precursor. Further, the present invention relates to an organic transistor using the above-described film forming an image. [Polyimine precursor] The present invention is an underlayer film for forming an image, which is characterized in that it contains a polyimine precursor having a repetitive structure represented by the following formula (1) or dehydration of the polyimine precursor. Polyimine obtained [Chemical 10]

R1OOC COOR2 (1)

• N—C—A—C—N—B. I II II I

Η OH OH (wherein A represents a tetravalent organic group 'B represents a divalent structure represented by the following formula (2) or (3) 'R^R2 independently represents a hydrogen atom or a monovalent organic group, and η represents a natural number ). In the above formula (1), R1 and R2 each independently represent a hydrogen atom or a monovalent organic group, and specific examples of the monovalent organic group are, for example, an alkyl group having 1 to 4 carbon atoms. -13- 201031687 The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a tert-butyl group. Among them, R1 and R2 are preferably a hydrogen atom. The structure of the organic group represented by A in the above formula (1) is not particularly limited as long as it is a tetravalent organic group. Further, the polyimine precursor may have one or a plurality of structures represented by the formula (1). Therefore, in the polyimine precursor, the organic group represented by A may be one type or a plurality of kinds. Wherein A is preferably a tetravalent organic group having an aliphatic ring or only an aliphatic group. More preferably, it is a tetravalent organic group having an aliphatic ring. Preferred examples of the organic group represented by A are exemplified by the organic groups of the following formulae A-1 to A-46. -14 - 201031687 [Table 1] [Table-1 Formula Al to Formula A-24] A-1 Α-2 h3c ch3 A-3 A-4 h3c ch3 .— — h3c ch3 A-5 介 A-6 A- 7 Female A-8 XX A-9 xc A-10 Α-Π A-12 3CWX A-13 : φχ A-14 : Two tuc A-15 A-16 A-17 A-18 ch3 A-19 A-20 ,ch3 A-21 V ch3 A-22 A-23 A-24 IK>^

[*2] [Table-1 Formula A-25] A-25 -15- 201031687 [Table 3] [Table-3 Formula A-25 to A-36] A-26 Α-27 Α-28 A-29 Α -30 Α-31 A-32 Α-33 Α-34 χΛχ A-35 Α-36 :01⁄2 [Table 4] [Table-4 Equations A-37 to A-46] Α-37 38 00C 39 00C Α-40 A-41 Α-42 D%tC h3c A-43 CH3 h3c Α-44 ch3 h3c A-45 Α-46 -16- 201031687 The above formulas A-1 to A-46 can be used as the underlayer film for forming an image. The characteristics required are appropriately selected. For example, in the above formulae A-1 to A-46, 'as a tetravalent organic group for improving the exposure sensitivity (in the present specification, the exposure sensitivity means the degree of self-hydrophobicity per unit of exposure amount (ultraviolet irradiation amount)) Listed as the 4 φ valent organic group having an aliphatic ring or only an aliphatic group of the formulae A-1 to A-25, the most effective organic group is exemplified as A-1, A-6, A-16 or A- 19. Further, the tetravalent organic group of the formulae A-1 to A-25 is also preferable from the viewpoint of improving the insulating effect. In the above formula (1), in the organic group represented by A, when the group other than the formula A-1 to A-25 is mixed, the ratio of the formulae A-1 to A-25 is preferably 10 mol% or more, more preferably 50 mol% or more, preferably 80 mol% or more 〇φ In the above formula (1), B represents a thiol ester bond having a side chain represented by the following formula (2) or formula (3) Price structure. By the thiol bond on the side chain of the polyimine precursor containing the repetitive structure represented by the formula (1) (or the polyimine thus obtained), when the thiol ester group is photodecomposed, The side chain of the thiol ester linkage will be cleaved from the polymer backbone. Therefore, by adjusting the hydrophilicity of the side chain bonded through the thiol bond, it is expected that the hydrophilicity and the like are changed by irradiation with light such as ultraviolet rays. 201031687 [化11] ο

II

S-c-χ-γ-ζ

In the above formula (2) or (3), X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms. Y represents a single bond, -0-, -COO-, -OCO-, -CONH-, -CH20-, -CH2CO〇- or -CH2CH2COO-. z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms, and any hydrogen atom may be substituted with a fluorine atom. R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. The structure of B represented by the above formula (2) or (3) may contain an aromatic carbocyclic ring in the side chain structure from the viewpoint of improving the absorption efficiency of ultraviolet rays. Therefore, in the above formula (2) or (3), when X represents a divalent aromatic group having 6 to 20 carbon atoms, preferred aromatic groups are phenyl, biphenyl, terphenyl, and naphthene. Base, stretch base, etc. The aliphatic hydrocarbon group having 3 to 26 carbon atoms in the above Z is exemplified by propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, a linear or branched alkyl group of a fluorenyl group, a second fluorenyl group, an isodecyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group or the like; an allyl group Alkenyl group such as alkenyl group; alicyclic -18-201031687 hydrocarbon group having cyclobutane, cyclopentane, cyclohexane, cyclodecane, steroid skeleton, adamantane, etc.; ethyl formate, methyl acetate, ethyl acetate Ester, methyl propionate, diacetyl, methyl isobutyrate, ethyl isobutyrate, ethyl butyrate, propyl butyrate, isobutyl acetate, isobutyl isobutyrate, butyl Isobutyl phthalate, isobutyl isovalerate, isoamyl acetate, isoamyl propionate, pentyl propionate, amyl isobutyrate, amyl butyrate, amyl isovalerate, allyl hexanoate Ethyl acetate, ethyl heptanoate, heptyl acetate, ethyl octanoate, stearyl acetate, decyl acetate, borneol acetate, ester of diethyl phthalate, etc. atom A linear alkyl group of 12 to 26 is used. Any hydrogen atom of the above aliphatic hydrocarbon group may be substituted by a fluorine atom, preferably an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom, preferably a linear fluorine having 4 to 7 carbon atoms. alkyl. Preferred examples of the B structure represented by the above formula (2) or (3) are as shown in the following [B-1] to [B-1 7]. Among these two-valent structures, from the viewpoint that the hydrophobicity is easily improved, it is preferably a structure of [B-13] to a two-valent structure, and more preferably a [B-15] to [B-17]. Indicates the two-valent structure. -19- 201031687 o:c ,S(CH2)k-CH3 \_(CH2)k-CH3

=11-17 S k=11-17 [B-1] -0- [B-2]

Jh3c ch3[called CH3 h3c ch3

[B-5] o:c -0- s^〇-(CH2)k-CH3 〇:C ° k=11-17 _irV- [S'6] [Chem. 13]

-20- 201031687 〇V〇^0^(CH2)k-CH3 s>〇-(CH2)k-CH3 ^ “η, l k=11-17 k=11-i7 [B-12]

.^CF3 S [化15]

[B-14] ^/(CF2)j-CF3 j=3-17

(CF2)j-CF3 1=3-17

FF FF FF ?O~(CF2) Bu CF3 [B-15] -6- [B-16 ] j=3-17 [B-17] Also 'considering other characteristics such as insulation, solvent solubility, When the film property and the adhesion of the film are also important characteristics, the polyimide precursor (and the polyimide obtained therefrom) used in the underlayer film for forming an image of the present invention may be in addition to the foregoing. In addition to the structure represented by the formula (1), the divalent organic group B in the above formula (1) is substituted with another divalent organic group D having no thiol ester bond in the side chain, and is represented by the following formula (4). Constructed polyimine precursor (and polyimine obtained therefrom). In this case, the divalent organic group B having a thiol ester bond in the side chain is represented by the above formula (the structure represented by 〇 and the other divalent organic group having no thiol ester bond on the side chain) (4) The bond of the structure may be any one of the block bond - 21,031,687 knot and/or random bond. [Chem. 16] (R1OOC COOR2 \ -N - C - C - N - D * 4 - (4 } I II II I / HO 〇H /m where A, R1 and R2 are the same as defined in the above formula (1), m represents a natural number, and D represents another 2 valence having no thiol ester bond in the side chain The polyimine precursor (and the polyimine obtained therefrom) used in the underlayer film for forming an image of the present invention, wherein D is a long-chain alkyl group in a side chain in the formula (4) When the ratio of the structure represented by the formula (4) (the structure having no thiol ester bond in the side chain) is excessively increased, the sensitivity to ultraviolet rays is lowered. Accordingly, when the structure represented by the formula (4) is included, The ratio of the structure represented by the formula (1) (the structure having a thiol ester bond in the side chain) is preferably 30 mol% or more. Further, in order to further improve the exposure sensitivity, the ultraviolet rays are shortened. It is necessary to further increase the content ratio of the structure represented by the formula (1), and the content ratio at this time is preferably 50 mol% or more. In the formula (4), 'D does not have a long-chain alkane in the side chain. In the case of the base, since the hydrophobicity of the film is mainly affected by the ratio of the structure represented by the formula (1), the structure represented by the formula (1) is determined in consideration of the surface tension of the image forming liquid or the adhesion to the upper member. In the structure represented by the above formula (2) or (3), when one part of the aliphatic hydrocarbon group of z is substituted by a fluorine atom, the ratio of the structure represented by the formula (n is 10) A high degree of hydrophobicity and sensibility can be obtained below 5% - 201031687 degrees. That is, it is considered that the change in the hydrophilicity of the membrane is caused by the decomposition/separation of the side chain structure in the ratio of the formula (1). When the molar concentration is 10 mol% or less, the exposure sensitivity does not necessarily decrease. In the above formula (4), the other divalent structure D having no thiol ester bond is preferably a structure having high insulating properties, and specifically, It is the structure of [D-1] to [D-57] described below. In the following [D-1] to [D-57], it is improved. From the viewpoint of the ease of insulation, φ is preferably a structure of [D-1] to [D-5]. Further, the structure having a high solvent solubility improving effect is listed as [D_2J, [D-5], [D]. -7], [D-8], [D-12], [D-22], [D-24] to [D-27], [D-29]. Also with a long chain alkyl group on the side chain Specific examples of the hydrophobic structure include the structures of [D-55] to [D-27]. However, as the characteristics of the organic transistor, improvement in insulation can be expected, and it can be used without reducing the sensitivity. When using, pay attention to the proportion of use. ❹ -23- 201031687 [Chem. 17]

Public [D-1 ] [ D-2 ]

Puzhong-b

[D-10] [D-11] [D-12] [D-13] [D-14] , ch3 H3Q PH, hQ-Q- [D-15] [D-16]

-24- 201031687 [Chem. 18]

Ο

Μ

[D-19] F3CvCF: 3 [D-22 ] [D-25 ] [ D-26 ]

[D-27 ]

-25- 201031687 [Chem. 19]

Φ

[D-41 ] [ D-42 ] [Chem. 20] -(CH2)ni-(n1 = 2 - 12) [D-43 ] ch3 ch3 -CH2-CH_(CH2)2—CH—(CH2)2 [ D-45 ] CH3 -(CH2)2_CH-(CH2)5 [D-47] (CH2)3—〇_(CH2)2—(CH2)3_ ch3 -(CH2)2—C—(CH2)2— [D-44] CH3 ch3 -(CH2)4—C—(CH2)3-

[D-46 ] CH3 ch3 —(CH2)4- CH_(CH2)5— [D-48 ] [D-49 ] -26- 201031687 [Chem. 21]

(CH2)n2 (η2 = 3 — 7) [D-51 ]

CH3 [D-53 ] (π5 = 11 / 17) 〇-(CH2)n5CH3 [D-55 ] (n6 = 4 — 6) ^^-〇-(CH2)n6CH3 [D-56]

[D-57] The above polyimine precursor is produced by, for example, polymerizing a tetracarboxylic dianhydride and a derivative thereof with a diamine. In particular, the polyimine precursor (polyglycine) represented by the following formula (5) is preferred because the reaction of the tetracarboxylic anhydride component and the diamine component as a raw material is relatively simple. [化22]

/ HOOC COOH (5)

N-C

I II Η Ο (wherein 'A, Β and η are the same as defined in formula (1)) "Quaternary acid dianhydride and its derivatives" Anhydride and its derivatives are not particularly limited, but -27-201031687 The tetracarboxylic dianhydride represented by the following formula (6) is preferably used. A in the formula is the same as defined in the above formula (1), and specific examples thereof are as shown in the above formulas A-1 to A-46. [化 23] Ο 〇

Ο 〇

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

As described so far, in the polyimine precursor, the organic group represented by A may be one type or a plurality of kinds may be mixed. Wherein A is preferably a tetravalent organic group having an aliphatic ring or only an aliphatic group, more preferably a tetravalent organic group having an aliphatic ring. Accordingly, the tetracarboxylic dianhydride component preferably contains a large amount of the compound of the formula (6) wherein A is a tetravalent organic group having an aliphatic ring or only an aliphatic group. More preferably, the compound of the formula (6) containing a large amount of A is a tetravalent organic group having an aliphatic ring, and preferably a polyiminoimine precursor is produced by using only an aromatic acid dianhydride, and the like is used as a lower layer for forming an image. In the case of a film, the insulating property tends to be remarkably lowered when a high electric field is applied to the underlayer film for forming an image. On the contrary, when an aliphatic acid monoanhydride is used, it is excellent in insulation properties in a cylindrical electric field. For example, in the case where the operating voltage of the organic transistor is about 1 MV/cm, it is preferable to use a fatty acid dianhydride as a raw material of the polyimide precursor in view of the insulating property. -28-201031687 "Diamine" In the present invention, the diamine used in the diamine component is represented by the following formula (7), and B is a structure represented by the following formula (2) or the following formula (3), that is, Specific examples of the divalent structure ° B having a thiol ester bond in the side chain are as shown in the above [B-1] to [B-17]. [Chemical 24] H2N-B-NH2 (7) ❹ [Chem. 25]

(R)t

〇 II S-C-X-Y-Z

(wherein, X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -〇-, -coo-, -OCO-, -CONH-, -CH20-, -ch2coo - Or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. Base, t means 〇 to an integer of 3). Further, in addition to the diamine represented by the formula (7), a diamine other than the formula (7) represented by the formula (q丨) may be used in the range in which the effects of the present invention are exhibited. H2N-D-NH2 (Q1) 'D in the formula (Q1) is the same as defined in the above formula (4). Here, a specific example of the diamine represented by the formula (Q1) is a diamine having a divalent structure represented by the above-mentioned [D-1] to [D-57] in the structure of D. [Synthesis method of diamine compound]

In the diamine represented by the above formula (7), the method of obtaining b as one of the structures of the formula (2) is not particularly limited. When an example is shown, a dinitro compound represented by the following formula (8) is synthesized, and a nitro group is converted into an amine group. The method for reducing the dinitro compound is not particularly limited. Usually, palladium-carbon, oxidized, nickel, iron, tin chloride, platinum black, lanthanum-alumina or the like is used as a catalyst, and ethyl acetate, toluene, and the like are used. A method in which a solvent such as tetrahydrofuran, dioxane or an alcohol is reacted with hydrogen, hydrazine, hydrogen chloride or ammonium chloride. In the present invention, a compound having a sulfur atom or the like in the skeleton of the dinitro compound may occasionally become catalytically toxic, and may inactivate the catalyst. Therefore, it is more preferable to use nickel hydride, iron, tin chloride or the like. Chemical reduction method. [2] 2:c-s-x_y-z<^-n〇2 (8)

(R)t (wherein 'X, Y, Z, R and t are the same as defined in the above formula (2)) The dinitro compound of the above formula (8) can be obtained by the following dinitro group It is obtained by reacting benzoyl chloride (9) with a compound containing a thiol group (1 〇). -30- 201031687 [2] o2n o=c -^-N02 ( 9 ) (R)t HS-XYZ (10) (wherein X, Y, Z, R and t are in the above formula (2) Same definition)

Among the diamines represented by the above formula (7), a method of obtaining a diamine having a structure of the formula (3) is not particularly limited. For example, a dinitro compound represented by the following formula (11) can be synthesized, and then obtained by subjecting a nitro group to an amine group in the same manner as in the case of the above dinitro compound (8).化2N<^r Ο .C-X-Y-Z 〇 N〇2 (11) (R)t

(wherein X, Y, Z, R and t are the same as defined in the above formula (3)) The dinitro compound of the above formula (11) can be represented by the dinitro group having a thiol group shown below The compound (12) is obtained by reacting with ruthenium chloride (1 3 ) having an aliphatic hydrocarbon which may also contain a fluorine atom. [化30] SH 〇2Ν&quot;ή&quot;Ν〇2 (12&gt; CI-EXYZ (13)(R)t -31 - 201031687 (wherein X, Y, Z, R and t are in the above formula (3) The definition of the same is as follows: "Method for producing polyimine precursor" A polyphthalimide precursor having a repeating structure represented by the formula (1) is obtained, and the tetracarboxylic acid represented by the above formula (6) is contained. The method of mixing and reacting the tetracarboxylic dianhydride component of the anhydride with the diamine component containing the diamine represented by the above formula (7) and, if necessary, the diamine component represented by the above formula (Q1) in an organic solvent is simple. A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent is exemplified by stirring a solution in which a diamine component is dispersed or dissolved in an organic solvent, and directly adding a tetracarboxylic dianhydride directly or a method of dispersing or dissolving it in an organic solvent; conversely adding a diamine component to a solution of dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; and mutually adding a tetracarboxylic dianhydride component and two Amine component method, etc. Further 'tetracarboxylic dianhydride component and diamine In the case where a plurality of compounds are present, the polymerization may be carried out by mixing the plurality of components in advance, or the polymerization may be carried out individually. The polymerization of the above polyimine precursor used in the present invention, tetracarboxylic acid The ratio of the acid dianhydride component to the diamine component, that is, the total mole number of the dicarboxylic acid di-gf component: <the total mole number of the diamine component> is preferably 1:0.5 to 1:1.5. Generally, the polymerization reaction is the same, and the molar ratio of the molar ratio is closer to 1: the greater the degree of polymerization of the U-branched U-batter produced by hydrazine, the greater the molecular weight. In the method for producing the polyimine precursor, the tetradecanoic acid is used. The dianhydride is -32-201031687. The temperature at which the diamine component is reacted in an organic solvent is usually from -20 to 150 ° C. Preferably, it is from 0 to 80 ° C. The polymerization temperature is set to a high temperature. It is carried out quickly and completely, but when it is too high, there is a case where a high molecular weight polyimine precursor cannot be obtained. Further, when the polymerization is carried out in an organic solvent, the two components in the solvent (tetracarboxylic anhydride component and diamine component) Solid mass concentration There is no particular limitation, but when the concentration is too low, it is difficult to obtain a high molecular weight polyimine precursor. When the concentration is too high, the viscosity of the reaction liquid is too high to be uniformly stirred, so it is preferably from 1 to 50% by mass, more preferably 5 to 30% by mass. It may be carried out at a high concentration in the initial stage of the polymerization, and then an organic solvent may be added together with the purification of the polymer (polyimine precursor). The organic solvent used in the above polymerization reaction is a polymer which can be dissolved. The quinone imine precursor is not particularly limited, but specific examples thereof include hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, and N-Φ methyl group. -2-pyrrolidone, N-methyl caprolactam, dimethyl sulfite, tetramethyl urea, pyridine, dimethyl maple, hexamethylarylene, r-butyrolactone and the like. These may be used singly or in combination of two or more. Further, even a solvent which cannot dissolve the polyimide precursor can be mixed in the solvent as long as it does not precipitate the formed polyimide precursor. The solution containing the polyimine precursor thus obtained can be used as it is in the formation of a film coating liquid which is formed below the image. Further, the polyimine precursor precipitate may be isolated and recovered in a weak solvent such as water, methanol or ethanol. -33- 201031687 [Polyimide] A polyimine precursor having a structure represented by the above formulas (1) and (4) (and the above formula (5)) can be made into a polyimine by dehydration ring closure . The method for the ruthenium imidization reaction is not particularly limited, but the imidization of a catalyzed ruthenium using a basic catalyst and an acid anhydride is less likely to cause a decrease in the molecular weight of the quinone imine during the ruthenium imidization reaction, and the ruthenium imidization The control of the rate is easier and better. The catalyst imidization can be carried out by stirring the aforementioned polyimine precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride for 1 to 1 hour. Further, the polyimine precursor may be used as it is (without isolation) a solution comprising a polyimide precursor obtained by polymerization of the above tetracarboxylic anhydride component and a diamine component. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate alkalinity in carrying out the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because it is easier to purify the polyimine obtained after the quinone imidization. As the organic solvent, a solvent used in the polymerization of the above polyimine precursor can be used. The reaction temperature in the imidization of the catalyst oxime is preferably from -20 to 250 t, more preferably from 0 to 180 °C. When the reaction temperature is set to a high temperature, the imidization is rapidly progressed, but when the reaction temperature is too high, the molecular weight of the polyimine is lowered. The amount of the basic catalyst is preferably from 0.5 to 30 moles, more preferably from 2 to 20 moles, relative to the acid amide group in the aforementioned polyimide intermediate. Further, the amount of the acid anhydride is from 1 to 50 moles, more preferably from 3 to 30 moles, relative to the acid amide group in the aforementioned polyimide intermediate. By adjusting the above reaction temperature and the amount of the catalyst, the yield of the obtained ruthenium imine can be controlled. The reaction solution of the solvent-soluble polyimine obtained as described above can be directly used for the production of the gate insulating film described later, but since the reaction solution contains a ruthenium-based catalyst, it is preferred to use a polyimide. Purified • Recycled • Washed. A convenient method for recovering polyimine is to pour the reaction solution into a weak solvent under stirring to precipitate the polyimine and filter it. The weak solvent to be used at this time is not particularly limited, and may, for example, be methanol, hexane, heptane, ethanol, toluene, water or the like. After the precipitate is recovered by filtration, it is preferably washed with the above weak solvent. Φ The recovered polyimine can be dried at room temperature or under reduced pressure to become a polyimide pigment at normal temperature or under heat. The polyimine powder is further dissolved in a good solvent, and reprecipitation is repeated in a weak solvent for 2 to 1 time, and impurities in the polymer can be further reduced. The good solvent to be used at this time is not particularly limited as long as it is a soluble polyimide precursor or a polyimine, but examples thereof are, for example, N,N-dimethylformamide, N,N-dimethyl Acetamide, 2_pyrrolidone, N-methyl-2-pyrrole, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methyl-35- 201031687 Base hexamethyleneamine, dimethyl sulfoxide, tetramethyl urea, pyridine, r-butyrolactone and the like. Further, when three or more kinds of weak solvents such as alcohols, ketones, and hydrocarbons are used as the weak solvent for the re-sinking chamber, the purification efficiency can be further improved. [Formation film coating liquid under the image formation] 下 The underlayer film for forming an image of the present invention can be formed by forming a film coating liquid under the image. The film coating liquid under the formation of the image may be a coating liquid containing the above-mentioned polyimide precursor, the above-mentioned polyimine, and a solvent, and if necessary, a coupling agent or a surfactant which will be further described, It is preferred to contain a polyfluorene imine precursor obtained by reacting a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine component containing a diamine represented by the formula (7). Or a coating liquid of the polyimine obtained by subjecting the polyimine precursor to dehydration ring closure. [化31] Ο 〇

H2N-B-NH2 (7}

(wherein A represents a tetravalent organic group, and B represents a divalent structure represented by the formula (2) or (3), -36 - 201031687 [Chem. 32]

(3) Ο ιι SCXY-2 R1 and R2 each independently represent a hydrogen atom or a monovalent organic group, a bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents '-COO- ' -OCO- ' -CONH - '-CH2〇- '-CH2COO -CH2CH2COO-, Z represents an aliphatic hydrocarbon group of a carbon atom which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, a carbon atom alkoxy group or an alkyl group having 1 to 3 carbon atoms The base, t represents 0 to 3, and preferably Z of the above formula (2) or (3) represents an aliphatic hydrocarbon group underlayer coating liquid having 3 to 26 carbon atoms substituted by any atom. The molecular weight of the guanamine precursor and/or polyimine used in the film coating liquid formed under the above-mentioned image formation is preferably used in view of stability such as solvent resistance at the time of formation of the operation (or poly ring). The weight average molecular weight (as a result of oxyethylene) is 2,000 to 200,000, more preferably 5,000 to 〇. The underlayer film is formed by using the above-mentioned layer film coating liquid under the image formation, and when irradiated with ultraviolet rays, regarding the hydrophilicity and hydrophobicity There is not much difference between the polyimine precursor and the polyimine. When the lower layer of the image is focused on this point, the imidization ratio and X represent the single bond, -Οι 3 to 26 The integer of 1 to 3), the atomic fluorine: the image of the 'representation of the polyether, the film polyethylene glycol GPC determination of 50,000 'for the portrait, the amount due to the resulting shape. No special limit -37 - 201031687 system. However, by using polyimine, it is possible to obtain a highly reliable film which can be fired at a low temperature (less than 180 ° C), which is a polyimine. Since the polarity of the precursor is low, the advantage of improving the water contact angle (which can improve the hydrophobicity) before the ultraviolet irradiation can be obtained, and therefore it is more preferable to use the polyimide. On the other hand, when the underlayer film coating liquid is formed in the underlayer film (for example, a gate insulating film) which is mainly used for forming an insulating layer, the coating solution has a yttrium imidation ratio of preferably 90%. the above. However, the ruthenium imidization ratio can be lowered without impairing the solvent solubility. However, in this case, when the film is formed, the lowermost layer is made into a high-yield imidization by using a blending method described later (high insulation). It is useful to retain high insulation as a lower film. The solvent to be used in the film coating liquid for forming the image layer described above is not particularly limited as long as it is a soluble polyimide precursor or a polyimide, and examples thereof include hydrazine, hydrazine-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-ethlyl-2-pyrrolidinium , N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, r-butyrolactone and other good solvents. These may be used singly or in combination, and a weak solvent such as an alcohol, a ketone or a hydrocarbon may be used in combination with the above-mentioned good solvent. The ratio of the solid content in the layer coating liquid to be formed in the image formation layer is not particularly limited as long as the components including the coupling agent to be described later are uniformly dissolved in the solvent, and are, for example, 1 to 30% by mass, for example, 5 to 2〇-38- 201031687% by mass. Here, the solid content means that the solvent is removed from all the components of the layer coating liquid under the formation image. The method for preparing the layer coating liquid under the formation of the image is not particularly limited, but a solution containing a polyimine precursor obtained by polymerization of the tetracarboxylic anhydride component and the diamine component described above may be used as it is or used. The reaction solution of the polyimine obtained by the solution. Further, in the layer coating liquid under the image formation described above, the coupling agent may be further contained in order to improve the adhesion between the Φ coating liquid and the substrate without impairing the effects of the present invention. The coupling agent may, for example, be a compound containing a functional decane or a compound containing an epoxy group, and specific examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2 -Aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-amine Benzyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyl φ triethoxy decane, N-ethoxycarbonyl- 3-Aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-trimethoxydecylpropyltriethylamine, N-triethyl Oxyalkylalkylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-tri Azadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N- Benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-I-propylpropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxy Baseline, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)-3_-39- 201031687 Aminopropyltrimethoxydecane, N-bis (oxyethyl) 3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 6-tetrahydration Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) a compound such as cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane. These may be used alone or in combination of two or more. When the coupling agent is used, the content thereof is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per part by mass of the film coating liquid under the formation of the image. Further, in the layer coating liquid for forming the image, the surfactant may be contained in order to improve the coating property of the coating liquid, the film thickness uniformity or the surface flatness of the film obtained from the coating liquid. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. Such surfactants are listed, for example, as F TOP EF301, EF303, EF352 (manufactured by Jam Co), MEGAFACE F171, F173, R-30 (manufactured by Otsuka Ink Chemicals Co., Ltd.), FLORARD FC430, FC431 (Sumitomo 3M Chemical Industry Co., Ltd., ASAHIGUARD AG7 10, SURFLON S-3 82, SC 1 0 1 , SC 1 02, SC 1 03, SC 1 04, SC105, SC106 (made by Asahi Glass Co., Ltd.). In the case of using the surfactant, the content is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer component contained in the film coating liquid under the formation of the image. [Related Polymer Phenomenon] The above-mentioned layered film coating liquid can be mixed with other polymer φ (for example, high insulation) which can form a film in addition to the above-mentioned polyimine precursor or polyimine. a polymer), in the form of a so-called polymer blend, by appropriately adjusting the polymer (the aforementioned polyimine precursor, polyimine and other polymers) The structure or the like can form a concentration gradient of the polymer in the thickness direction of the film when the underlayer film for image formation is formed, and thus can be utilized as a useful means. For example, in order to cause a change in the hydrophobicity of the film mainly on the surface of the film, as far as this is concerned, the above-mentioned layer having a thiol bond in the side chain exists only on the layer (surface layer) φ of the underlayer film for forming an image. The imine precursor and/or polyimine can be used. Therefore, when the film formation liquid under the formation of the image forming film is in the form of a polymer blend (hereinafter, the coating liquid of the form is referred to as a blend coating liquid), the polyimine precursor or the poly The blending ratio of the quinone imine is 1% by mass to 100% by mass in the solid content of the blend coating liquid. When it is 1% by mass or less, it is difficult to completely cover the outermost surface of the film when the blend coating liquid is formed on the film, and the ability to form an image is deteriorated. The above-mentioned polymer blend is useful, for example, in the case where a gate insulating film for forming an image is used in the use of a gate insulating film which is required to have a high insulating property of -41 - 201031687. When it is used for a gate insulating film, the coating liquid is required to have a firing temperature corresponding to 1 80 ° C or lower, a film formation by coating, and a solvent resistance to an organic semiconductor coating liquid (xylene, Various properties such as a low solvent such as trimethylbenzene and a low water absorption rate, but the performance required for insulation is particularly high. In order to achieve such high insulation properties, the imidization ratio of the film coating liquid formed under the above-described image formation layer is at least 80% or more, and may be required to be 90% or more depending on the case, but conversely, the sulfhydrylation ratio exceeds 90%. Solubility is lost when it is above %. In this case, by providing only a layer having a high insulating property in the lowermost layer of the insulating film, the layer formed by the layer coating liquid under the image formation described above is in the upper layer, and the insulating property of the insulating film can be maintained. It also eliminates solubility problems. As described above, in order to form the lower layer of the lower layer film for forming an image as a high insulating layer, and the upper layer is a hydrophilic/hydrophobic conversion layer, the layers may be laminated in this order, but the operation is rather complicated. At this time, the material of the high insulating layer is mixed with the material of the hydrophilic-hydrophobic conversion layer (that is, the aforementioned polyimine precursor and/or polyimine), and at this time, if the polarity or molecular weight of the upper material is lower than the lower layer If the mixture is coated on a substrate and dried to evaporate the solvent, the above-mentioned concentration gradient (herein referred to as layer separation) can be easily controlled by the action of forming the layer by moving the upper layer material to the surface. . The material for forming the high insulating film of the lower layer described above is preferably a soluble polyimide. When a soluble polyimine is used as the underlayer material, from the viewpoint of the insulating property of -42 to 201031687, it is preferred that the sulfhydryl imidization ratio of the polyimine in the solution is high, at least 50% or more. It is 80% or more, preferably 90% or more. Other materials which can be used as the underlayer material are exemplified by general organic polymers such as epoxy resin, acrylic resin, polypropylene, polyvinyl alcohol, polyvinyl phenol, polyisobutylene, and polymethyl methacrylate. The preferred soluble polyimine is exemplified by a soluble polyimine consisting of one or a plurality of structures selected from the group consisting of the structures of the formula (1 6 ) 0 . [化33]

(In the formula, A represents an aliphatic ring or a tetravalent organic group composed only of an aliphatic group, and D represents a divalent organic group). The molecular weight of the above-mentioned soluble polyimine is preferably a weight average molecular weight (as a result of GPC) in terms of polyethylene glycol (or polyethylene oxide), preferably from 2,000 to 200,000, more preferably from 5,000 to 50,000. In (16), specific examples of A are exemplified by a tetravalent organic group selected from A-1 to A-25, and specific examples of D are exemplified as D-1 to D-57. Among them, 'the best A's structure is A-5, A-6, A-16, A-18, A-19, A-20, A- from the viewpoint of high solubility of soluble polyimine. 21. The structure of the 4-valent organic group 'D of A-22 and A-25 is D-7, D-8, D-9, D-12, D-19, D-20, D-22, D-29 2, D-39, D-41, D-42 2 -43- 201031687 organic base. The soluble polyfluorene 〇 〇 , 〇 有机 有机 有机 有机 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Application film 1 and the use of a dipping method, a rotary ink method, a spray method, and a brush coating liquid are applied to a polyethylene substrate, a polyether mill, a plastic substrate for polysilicon, or glass for pre-drying. The formation is formed to form an underlayer film for forming an image. In the above-mentioned heat-treated square plate or oven, the firing temperature in a suitable atmosphere, vacuum or the like is promoted, preferably from 180 ° C to imine, which may be used alone or in combination of plural kinds of use. For example, when the film thickness is required to be 40 〇 nm, the upper layer (hydrophobic hydrophobic conversion layer) of the amine precursor and/or the polyimine may be used in an amount of 1% by mass or more. When there is too little, there is a case where there is a large deviation in the form of the image. Preferably, the method for producing a film is a coating method, a transfer printing method, a roll coating method, a spray coating, or the like, and the above-mentioned underlayer film, polyethylene, polycarbonate, and polyterephthalic acid are formed. Ethylene naphthalate, polyimine, and the like are widely used on a substrate or the like, and then coated on a hot plate or an oven. The patterning method for forming the image by the underlayer film or the insulating film by heating the coating film is not particularly limited, and may be exemplified by using an inert gas such as air or nitrogen gas in the heating surrounding gas. The viewpoint of the thermal imine imine of the polyimide precursor is 250 ° C, and it is preferably 180 ° C or less from the viewpoint of film formation on a plastic substrate -44 - 201031687. It is also possible to use a temperature change of two or more stages for firing. The staged firing can further improve the uniformity of the resulting film. When the underlayer film for forming an image is formed, the film coating liquid under the image formation can be directly used for coating the substrate because it is in the form of a polyimide precursor and/or a polyimide and the solvent. In order to adjust the concentration, or to ensure the flatness of the coating film, or to improve the wettability of the coating liquid to the substrate, the surface tension of the coating φ liquid, the polarity, the boiling point adjustment, etc., the above solvent may be added, and the others may be added. Various solvents are used as the coating liquid. Specific examples of such solvents include, in addition to the solvent described in the first paragraph of the above-mentioned specification, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl card. Alcohol acetate, ethylene glycol, etc., 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate φ, dipropylene glycol , propylene glycol derivatives such as 2-(2-methoxypropoxy)propanol, 2-(2-ethoxypropoxy)propanol and 2-(2-butoxypropoxy)propanol A lactic acid derivative such as methyl ester, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate. These can be used alone or in combination. Further, from the viewpoint of improving the preservability of the coating liquid and the uniformity of the film thickness of the coating film, preferably 20 to 80% by mass of the total amount of the solvent is selected from N,N-dimethylformamide, N,N- At least one solvent of dimethylacetamide, N-methyl-2-pyrrolidone, r-butyrolactone, dimethylhydrazine. The concentration of the coating liquid is not particularly limited, but the solid concentration of the polyimine precursor and the poly-45-201031687 quinone is preferably from 0.1 to 30% by mass, more preferably from 1 to 10% by mass. These can be arbitrarily set by the specification of the coating device or the resulting film thickness. When the underlayer film for forming an image of the present invention produced as described above is used as the underlayer film for forming an image, if the film thickness is too thin, the pattern property after ultraviolet irradiation is lowered, and if it is too thick, the surface uniformity is impaired. Accordingly, the film thickness is preferably from 5 nm to 100 nm, more preferably from 10 nm to 300 nm, most preferably from 20 nm to 100 nm. Further, the underlayer film for forming an image of the present invention can also be used as an insulating layer in the case where the insulating property is sufficiently high. The membrane functions. In this case, the underlayer film for forming an image is used as a gate insulating film directly on the gate electrode, for example, in an organic FET device. In this case, the film thickness of the underlayer film for forming an image is preferably thicker than that of the underlayer film for forming the image. The film thickness is preferably from 20 nm to 100 nm, more preferably from 50 nm to 800 nm, and most preferably from 10 nm to 500 nm. [Method for Producing Electrode for Forming Image] The underlayer film for forming an image of the present invention is irradiated in a pattern Ultraviolet rays, then, by applying an image forming liquid described later, an electrode for forming an image can be produced. In the present invention, the method of irradiating ultraviolet rays in the form of the lower layer film for forming the image is not particularly limited, and is, for example, a method of irradiating with a mask having an electrode pattern, and a method of drawing an electrode pattern using laser light. Wait. -46- 201031687 The material or shape of the above mask is not particularly limited as long as the necessary area of the electrode is transmitted through the ultraviolet ray, and the area other than the ultraviolet ray is not transmitted. At this time, the wavelength of the ultraviolet light used is usually in the range of 200 nm to 5 Å Onm, and it is preferable to select an appropriate ultraviolet wavelength which is suitable for the type of the underlayer film for forming an image to be used. Specifically, wavelengths of 248 nm, 254 nm, 303 nm, 313 nm, and 365 nm are listed. It is preferably 248 nm or 254 nm. In the formation of the image of the present invention, the surface of the lower layer film is slowly increased by ultraviolet irradiation, and the surface is saturated with sufficient irradiation amount. This increase in surface energy causes a decrease in the contact angle of the image forming liquid, and as a result, the wettability of the image forming liquid in the ultraviolet ray irradiation portion is improved. According to this, when the image forming liquid is applied to the underlayer film for forming an image of the present invention after ultraviolet irradiation, the image forming liquid forms a self-organized shape along the pattern shape drawn by the surface energy difference on the underlying film for forming the image. With the pattern, an electrode of any shape can be obtained. According to this, it is necessary to sufficiently change the contact angle of the image forming liquid to the ultraviolet irradiation amount of the underlayer film for forming an image. However, in terms of energy efficiency and time for shortening the manufacturing step, it is preferably 20 J/ Below Cm2, it is more preferably l〇J/cm2 or less, and most preferably 5 J/cm2 or less. Further, the larger the difference in the contact angle between the ultraviolet ray irradiated portion forming the lower layer film for the image and the image forming liquid in the unirradiated portion, the easier the patterning is, and the electrode can be processed into a complicated pattern or a fine pattern. Therefore, the amount of change in contact angle caused by ultraviolet irradiation is preferably 5 or more, more preferably 10 or more, and most preferably 20 or more. For the same reason, the contact angle of the preferred image forming liquid is 30° or more in the ultraviolet ray-free period from -47 to 201031687, and is 20° or less in the ultraviolet ray irradiation unit. Further, since water is often used as the solvent for the image forming liquid, the performance evaluation of the underlayer film can be easily evaluated by changing the contact angle of the image forming liquid in accordance with the amount of change in the contact angle of water. The image forming liquid in the present invention is a coating liquid which can be used as a functional film by evaporating the solvent contained therein after being applied onto a substrate, and is, for example, dissolved or uniformly dispersed in a charge transporting substance. It is made up of at least one solvent. Here, the charge transport property is synonymous with conductivity, and means any one of hole transportability, electron transport property, and electron and electron transport properties. The charge transporting substance is not particularly limited as long as it has conductivity capable of transporting holes or electrons. Examples thereof are metal fine particles such as gold, silver, copper, aluminum, or inorganic materials such as carbon black, fullerenes, and carbon nanotubes, or polythiophenes, polyanilines, polypyrroles, polyfluorenes, and derivatives thereof. Such as organic π conjugated polymers and the like. Further, in order to increase the charge transporting ability of the charge transporting substance, a halogen, a Lewis acid, a protonic acid, or a transition metal compound may be further added to the image forming liquid (specific examples are Br2, I2, Cl2, FeCl3, MoC15, BF3, and asf5). , charge accepting substance such as so3, hno3, H2S04, polystyrenesulfonic acid, etc.' or an alkali metal or an alkyl group (specific examples are Li, Na, K, Cs, tetraethylammonium, tetrabutyl) A charge supply substance such as ammonium or the like is used as a dopant. The solvent of the image forming liquid is not limited as long as it can dissolve or uniformly disperse the above-mentioned charge transporting substance or dopant. However, from the viewpoint of obtaining a correct electro-type pattern, it is preferable to display a sufficiently large contact angle with respect to the ultraviolet non-irradiated portion forming the underlayer film for image formation, and to form an underlayer film for the image forming of the present invention. In terms of less damage, it is preferably water or various alcohols. Also 'N,N-dimethylformamide, N,N-dimethylacetamide, 2-pyrrolidine, N-methyl-2-pyrrolidone, N-ethyl-2- Polar solvents such as pyrrolidone, N-vinyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sub-milling, and tetramethyl urea are also excellent in solubility in organic charge transporting substances. It is preferable from the viewpoint of exhibiting a sufficiently large contact angle with respect to the ultraviolet non-irradiated portion of the underlayer film for image formation, but these are preferably used in the range which minimizes damage to the underlayer film for forming an image of the present invention. The concentration of the charge transporting substance in the image forming liquid is preferably 〇. 〇 i to 30% by mass ‘more preferably 〇 to 10% by mass, preferably 1 to 5% by mass. Specific examples of the image forming liquid of the present invention include Baytron (registered trademark) P (polyethylidene dioxythiophene, manufactured by Bayer Co., Ltd.). φ The electrode of the present invention is produced by applying the above-mentioned image forming liquid to the underlayer film for forming an image of the present invention, forming a pattern, and evaporating the solvent. The evaporation method of the solvent is not particularly limited, but it can be evaporated by using a hot plate or an oven in an appropriate atmosphere, that is, an inert gas such as air or nitrogen, or a vacuum to obtain a uniform film formation surface. The temperature of the solvent to be evaporated is not particularly limited, and is preferably carried out at 40 to 250 t:. From the viewpoint of maintaining the shape of the pattern and uniformity of the film thickness, it is also possible to use a temperature change of two or more stages. The electrode formed of the image forming liquid can be used not only as a wiring for connecting electronic devices of the connection -49-201031687, but also as an electronic device such as an electric field effect transistor, a bipolar transistor, various diodes, or various inductors. Electrodes, etc. The electronic device of the present invention is the electrode having the above-described present invention. The following is an example in which the underlayer film for forming an image of the present invention is used in an organic FET device, but the present invention is not limited to these. First, a highly doped n-type germanium substrate is prepared. Preferably, the substrate is preliminarily cleaned by washing with a lotion, alcohol, pure water or the like, and subjected to surface treatment such as ozone treatment or oxygen-plasma treatment before use. SiO 2 , Ta 205 , Α 12 〇 3 or the like is formed on the substrate by thermal oxidation, sputtering, CVD _ , vapor deposition, or the like to form a gate insulating film. The film thickness of the gate insulating film varies depending on the use of the organic FET, but it is preferably in the range of 30 nm to 100 nm in terms of driving voltage and electrical insulating properties. Next, a layer containing a polyimide precursor having a repeating structure represented by the above formula (1) and/or a polyimide is formed on the insulating film in the above-described order. The film thickness of the layer is preferably from 20 nm to 100 nm. Subsequently, ultraviolet rays are irradiated using a mask or the like for obtaining a desired electrode shape. @ Next, an image forming liquid using a polar solvent such as water is applied onto the surface of the underlayer film for forming an image. The applied image forming liquid repels the hydrophobic portion (ultraviolet-irradiated portion) and accelerates to the hydrophilic portion (ultraviolet irradiation portion) to be stabilized and dried to form a patterned source and a drain electrode. The coating method of the image forming liquid is not particularly limited to a spin coating method or a casting method, but is preferably an ink jet printing method or a spray coating method which is easy to control the amount of liquid. Finally, the organic semiconductor material such as pentacene or polyolefin of the active layer of the organic FET is formed into a film. The film formation method of the organic semiconductor material is not particularly limited, and examples thereof include vacuum deposition or spin coating of a solution, a casting method, an inkjet printing method, or a spray coating method. Such an organic FET can be greatly reduced in manufacturing steps, and an organic FET having a shorter channel than the mask evaporation method can be fabricated. Therefore, when a low mobility organic semiconductor material is used as an active layer, a large current may be taken out. . Further, since the underlayer film for forming an image obtained by the method of the present invention also has excellent electrical insulating properties, it can also be used as a gate insulating layer, and the manufacturing step can be simplified. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. [Measurement of Number Average Molecular Weight and Weight Average Molecular Weight] The number average molecular weight (hereinafter referred to as Μη) and the weight average molecular weight (hereinafter referred to as Mw) of the chitosan precursor obtained by the following synthesis examples are GPC (normal temperature). The gel permeation chromatograph "is measured by the following apparatus and measurement conditions, and calculated by polyethylene glycol (or polyethylene oxide). GPC device: shodex (registered trademark) (GPC-101) manufactured by Showa Denko Electric Co., Ltd. Pipe column: Sh〇dex (registered trademark) manufactured by Showa Denko (share) (KD803, KD805 series)

Column temperature: 50 ° C Dissolution: N,N-dimethylformamide-51 - 201031687 (as additive: lithium bromide-hydrate (LiBr · H20) 30mmol / L, phosphoric acid • anhydrous crystals (〇-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10 ml/L) Flow rate: 1.0 ml/min. Measured wire for standard sample: TSK standard polyethylene oxide manufactured by TOSOH (molecular weight): molecular weight: about 900,000, 1 50,000 '100,000 &gt; 30,000 )

Polyethylene glycol manufactured by Polymer Laboratory (molecular weight ^: about 1 2,000, 4,000, 1,000) [Measurement of film thickness] The film thickness of the polyimide film is a part of the film peeled off by a cutter, and it is fully automatic. The fine shape measuring machine (manufactured by 坂硏 坂硏 坂硏 ( ( , , , , , , , , , , 测定 测定 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 ❿ [Ultraviolet Irradiation] Ultraviolet light is transmitted through a band-pass filter on a polyimide film at a wavelength of 254 nm using a high-pressure mercury lamp as a light source. Further, the amount of exposure on the polyimide film was measured by an illuminometer (manufactured by OAI Corporation, MODEL 306), and was attached to a Deep UV probe having a peak sensitivity of 253.7 nm to measure the illuminance of ultraviolet rays. The obtained illuminance was 45 to 50 mW/cm2. The obtained illuminance is multiplied by the exposure time as the exposure amount (J/cm2). -52- 201031687 [Measurement of contact angle] The contact angle is measured in a constant temperature and humidity environment (2 5 C ί 2 C, 50% RH ± 5%) using a fully automatic contact angle meter CA-W (Concord Measured by Interface Chemical Company). The contact angle of water is determined by the liquid amount 3 # L ' after standing for 5 seconds, and the contact angle of propylene glycol monomethyl ether (PGME) is determined by the liquid amount of 3.0~3.5 β L, and after standing for 5 seconds, the liquid is measured. . <Synthesis Example> [Synthesis Example 1: Synthesis of diamine compound (deuterated-1:3,5-diaminothiobenzoic acid octadecyl ester)] [Chem. 34]

[Hi]

Cooling the solution of the compound [丨丨] (20.0 (^, 6 9.79111111〇1), triethylamine (8.07 g, 79.76 mmol) in tetrahydrofuran (I55g) to 10 ° C under a nitrogen atmosphere, and Note that a solution of the compound [i] (15_3 3g '66.47mxn〇l) in tetrahydrofuran (70g) was added dropwise while the mixture was added. After the end of the addition -53- 201031687, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. (High-speed liquid chromatography) After confirming the completion of the reaction, the reaction liquid was drained and poured into distilled water (1.8 L), and the precipitated solid was filtered, washed with water, and then washed with methanol (i92 g) to obtain a compound [iii] (yield: 26.4 g, yield: 83%). 'H-NMR (400 MHz &gt; CDC13 &gt; δ ppm ) : 9.21-9.20 (1H &gt; m ), 9.07-9.06 ( 2H, m ) , 3 .1 8 ( 1 2 H,t ) ,1 · 7 3 - 1.6 7 ( 2H,m ) &gt; 1.48 - 1.3 7 ( 2H &gt; m ) , 1.23 ( 28H, s) , 0.86 (3H, t ). Under a nitrogen atmosphere, After heating 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) to 70 ° C, ammonium chloride was added dropwise. 10% of (6.6 6 g, 124.5 mmol) After confirming the completion of the reaction by ΗPLC, the solid was filtered through celite, washed with 200 mL of ethyl acetate and distilled water, and then the aqueous layer was removed, and the organic layer was washed three times with distilled water (300 mL). After drying over anhydrous magnesium sulfate, the solvent was evaporated, and the crude product was crystallized from methanol (1 g 4 g) to give compound (DA-1) (yield: 11.7 g, yield Rate: 67%). 1 Η-NMR (400MHz ' CDC13,6 ppm ) : 6_69 ( 2H,dd) ' 6.18 ( 1H,t) , 3.69 ( 4H,brs ) ,3.00 ( 2H,t ),

1.66- 1 .56 ( 2H,m ) , 1 · 4 2 -1 · 2 5 ( 3 0 H,m ) , 0.88 ( 3H ,t ) 0 -54- 201031687 [Synthesis Example 2: Polyimine Synthesis of Precursor (PI-1) The octadecyl 3,5-diaminooxybenzoate (DA-1) prepared in Synthesis Example 1 was placed in a 50 mL four-necked flask under a nitrogen stream. g (0.003 mol), after dissolving in 10.42 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), adding 0.5766 g (〇.〇〇3 mol) of 1,2,3,4-cyclobutane The alkanetetracarboxylic anhydride (hereinafter referred to as CB DA) was stirred at 23 ° C for 10 hours to carry out a polymerization reaction, and then diluted with NMP to obtain an 8 mass% solution of the polyimine precursor (PI-1). The number average molecular weight (?η) and the weight average molecular weight (Mw) of the obtained polyimine precursor (PI-1) were Mn = ll, 650' Mw = 28, 380, respectively [Synthesis Example 3: Polyimine precursor (PI) -2) Synthesis] Under a nitrogen flow, DA-1 0.8 835 g (0.002 1 mol) and p-phenylenediamine (p-PDA) 0.0973 g (0.0009 mol) were placed in a 50 mL four-necked flask and dissolved in 8_83 g. After NMP, 0.5766 g (0.00294 mmol) of CBDA was added, and the mixture was stirred at 23 ° C for 10 hours to carry out polymerization, and then diluted with NMP to obtain a 6 mass % solution of the polyimine precursor (P1-2). . The number average molecular weight (?η) and weight average molecular weight (Mw) of the obtained polyimine precursor (PI-2) were Mn = 34,670, Mw = 97,560, respectively [Synthesis Example 4: Polyimine precursor (PI-3) Synthesis] -55- 201031687 1 5.065 g (0.040 mol) of 1-octadecyloxy-2,4-diaminobenzene (APC18) was dissolved in a 200 mL four-necked flask under a nitrogen stream. After 127.6 g of NMP, 7.45 g (0.038 mol) of CBDA was added to make it at 23. (: stirring for 12 hours to carry out polymerization, and then diluted with NMP to obtain a 6 wt% solution of the polyimine precursor (PI-3), the number average molecular weight of the polyimine precursor (PI-3) obtained (Mn) And weight average molecular weight (Mw) are Mn=16,000' Mw = 48,000, respectively [Synthesis Example 5: Diamine compound (DA-2)] Synthesis of DA-2 [Chem. 35]

6^13

The compound [iv] (42.63g &gt; 209.9mmol), the compound [v] (1 0 2.9 7 g '2 3 0 · 9 mm 01 ), copper powder (29.3 5g, 46 1) were stirred at 120t under a nitrogen atmosphere. · 8mmol), 2,2 '-bipyrrole (3 · 2 8 g ' -56- 201031687 20.99mmol ), a mixture of dimethyl alum (341g). After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (273 g), and filtered, and the filtrate was washed with distilled water (2 L) and ethyl acetate (1.5 L). Then, hexane (500 g) was added to the filtrate, and the organic layer was washed three times with saturated brine (1 L) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered and evaporated to give Compound [vi] (yield: 75.33 g, yield: 81%). W-NMR (400 MHz, CDC13, δ ppm): 7.48 (2 Η, d), ❹ 7.32 (2H, d), 2.52 (3H, s). Add N-fluoro-Ν'-(chloromethyl)triethylenediamine bis (0.1g, Tetrafluoroborate) (43.63 g, 123.2 mmol) was reacted at 23 °C. After confirming the completion of the reaction by HPLC, the solvent was distilled off. Next, dichloromethane (1.2 L) was added, and a saturated aqueous solution of sodium hydrogencarbonate (7 mL) was added in small portions. After the aqueous layer was removed, the organic layer was washed three times with saturated brine (? Subsequently, the solvent was distilled off by filtration to obtain a compound [vii] (yield: 48.05 g, yield: 89%). 'H-NMR (400 MHz * CDC13 » δ ppm ) : 7.81 ( 2H ' d ), 7·78 ( 2H, d ) , 2·71 ( 3H, s ). Acetic anhydride (46.39 g '454.4 mmol) was added to the compound [vii] (26.03 g, 56.8 mmol) under a nitrogen atmosphere, and the reaction was carried out under reflux with heating. After confirming the completion of the reaction by HPLC, the solvent was distilled off to obtain a crude product of the compound [Viii]. The obtained crude product was purified by column chromatography (SiO 2 , hexane / ethyl acetate) to yield compound [viii] (yield: 24.1 lg, yield: 85%). *H-NMR (400MHz « CDC13 5 δ ppm) : 7.54 ( 4H,s), 5.50 ( 2H,s ) , 2.14 ( 3H,s ). Under a nitrogen atmosphere, a 28% aqueous ammonia solution (13.73 g) was added to a solution of the compound [viii] (3 7.67 g, 75.3 mmol) in methanol (15 g), and stirred at 23 °C. After confirming the completion of the reaction by HPLC, the pH was adjusted to 6 with 35% hydrochloric acid, and then the solvent was evaporated. Subsequently, the crude product was dissolved in dichloromethane (1 L), washed three times with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered and distilled off to obtain Compound [ix] (yield: 31.28 g, yield: 97%). iH-NMR (400MHz, CDC13, (5 ppm): 7.44 (2H, d), 7.37 (2H, d), 3.61 (lH, s). Under a nitrogen atmosphere, compound [ix] (3 1.00g, 72.4 mmol), a solution of triethylamine (7.33 g, 72.4 mm 〇l) in tetrahydrofuran (139 g) was cooled to below 10 ° C, and tetrahydrofuran containing compound [i] (15_90 g '68.95 mmol) was added dropwise while paying attention to heat. (l〇〇g) solution. After the completion of the dropping force □, the reaction temperature was raised to 23 ° C, and the reaction was further carried out. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1.9 L), and the precipitate was separated by filtration. The solid was washed with water and recrystallized from 2-propanol (2 5 7 g) to give compound [X] (yield: 27.01 g yield: 63%). -58- 201031687 • H-NMR (400 MHz) &gt; CDC13 &gt; δ ppm) : 9.30 ( lH,t), 9. 1 5 ( 2H,d ) &gt; 7.74 ( 4H &gt; q ). Stir at 23 ° C in the presence of hydrogen in a nitrogen atmosphere. a mixture containing the compound [X] (14.00g' 22_5mmol), 3% platinum-carbon (supporting 0.3% iron, water '2.8g' 20wt%), and methanol (21〇g). After confirming the reaction by HPLC, The reaction mixture was filtered through diatomaceous earth to The diatomaceous earth was washed with an alcohol (5 0 φ mL ), and the solvent was distilled off. The crude product of the obtained compound (DA - 2 ) was washed with 2-propanol (60 g), filtered, and dried to obtain a compound (DA). -2) (yield: 9.13 g, yield: 72%). 'H-NMR (400 MHz · CDCI3 &gt; δ ppm) : 7·65 ( 4H , s), 6.73 ( 2H, d) , 6.24 ( 1H, t), 3.76 (4H, brs) [Synthesis Example 6: Diamine compound (DA-3)]

Synthesis of DA-3 [Chem. 36]

CtF17l liv] lx Hi]

[xiv]

[x m

-59 201031687 The compound [iv] (27.05 g '133.2 mmol), the compound [xi] (80.00 g, 146.5 mmol), copper powder (18.62 g, 293.0 mmol), 2, were stirred at 120 ° C under a nitrogen atmosphere. A mixture of 2'-bipyridyl (2 · 0 8 g, 13.32 mmol) and dimethyl submilling (216 g). After confirming the completion of the reaction by HPLC, the reaction mixture was poured into distilled water (1, 73 g), filtered, and the filtrate was washed with distilled water (1 L) and ethyl acetate (1 L). Next, hexane (500 g) was added to the filtrate, and the organic layer was washed three times with saturated brine (1 L) and dried over anhydrous magnesium sulfate. Subsequently, the solvent was filtered off and the solvent was evaporated to give compound [xii] (yield: 65.72 g, yield: 91%). &quot;H-NMR (400 MHz &gt; CDC13, δ ppm): 7.58 (2Η,d), 7.47 ( 2H,d), 2.54 ( 3H,s ). Add N-fluoro-N'-(chloromethyl)triethylenediamine to a solution of compound [xii] (50.00 g, 92.21 mmol) in acetonitrile (333 g) / purified water (17 g) under nitrogen atmosphere. Bis(tetrafluoroborate) (32.67 g, 92.2 1 mmol) was reacted at 23 °C. After confirming the completion of the reaction by ηPLC, the solvent was distilled off. Next, dichloromethane (800 mL) was added, and a saturated aqueous solution of sodium hydrogencarbonate (500 mL) was added in small portions. After removing the aqueous layer, the organic layer was washed three times with saturated brine (500 mL) and dried over anhydrous magnesium sulfate. Subsequently, solvent distillation was carried out by filtration to obtain a compound [xiii] (yield: 47.98 g, yield: 93%). 1H-NMR (400MHz ' CDCI3 ' &lt; 5 ppm ) : 7.81 ( 2H,d ), 7.77 (2H,d) ,2.78(3H,s) 〇201031687 under nitrogen atmosphere in compound [xiii] (70.63g) Trifluoroacetic anhydride (220.56 g, 1.05 m〇l) was added thereto, and the reaction was carried out. After confirming the completion of the reaction by HP LC, the crude product was distilled. Next, methanol (226 g) and triethylamine were added, and after stirring at 23 ° C for 30 minutes, the solvent was distilled off (ethyl acetate) (1 L) to dissolve the obtained crude product, followed by saturated φ (1 L) and saturated salt. After washing twice with water (1 L), magnesium was dried and the solvent was distilled off to obtain compound [xiv] (yield: 97%). 'H-NMR (400 MHz » CDC13 5 δ ppm): 7.44 7.36 ( 2H &gt; d ) , 3.61 ( 1H, s ). The solution containing the compound [xiv] (69. mmol) 'diethylamine (13.22 g, 130.62 mmol) φ 290 g) was cooled to 1 (TC or less) under a nitrogen atmosphere while paying attention to the heating edge [i] (28.68 g). , 124.40 mmol) of tetrahydrofuran (after the completion of the dropwise addition, the reaction temperature was raised to 23 ° C, and after confirming the completion of the HPLC, the reaction solution was poured into a distillation 7 J, and the precipitated solid was filtered, washed with water, from 2-propane. Alcohol (crystal, obtained compound [xv] (yield: 7 7.99 g, yield: 'H-NMR (400 MHz &gt; CDCI3 &gt; δ ppm ) : 9.27 9.1 7 ( 2H « d ) , 7.61 ( 4H,q ). 1 2 6.5 mmol of the solvent was heated under reflux to obtain (211.89 g). Next, the aqueous solution of the aqueous solution of ammonium bromide was used as sulfuric acid: 64.7 g to produce (2H, d), 00 g, 130.62 tetrahydrofuran (: dropwise addition of compound 1 4 5 g ) The solution was reacted with i. (8 g of 270 g in (3.5 L)). (1 Η, t ), -61 - 201031687 Stirring at 23 ° C in the presence of hydrogen under a nitrogen atmosphere a mixture of compound [xvii] (8.00 g, 11 mmol), 3% molybdenum-carbon (supporting 0.3% iron, water, 1.6 g, 20 wt%), methanol (120 g). After that, the reaction mixture was filtered through celite, and the celite was washed with methanol (30 mL), and the solvent was distilled off. The crude product of the obtained compound (DA-3) was washed with 2-propanol (28 g) and washed. Filtration and drying gave Compound (DA-3) (yield: 5.6 g, yield 76%). H-NMR (400 MHz » CDC13 &lt;5 ppm): 7.65 ( 4H, s), 6.73 (2H,d), 6.24 (1H,t), 3.76 (4H,brs). [Synthesis Example 7: Diamine compound (DA-4)] t) Synthesis of A-4 [Chem. 37]

[DA-4] A solution of the compound [xvi] (21.87 g, 45.54 mmol) and diethylamine (4_61 g, 45.54 mmol) in tetrahydrofuran (90 g) was cooled to below lor under a nitrogen atmosphere. A solution of the compound [i] (10.Og' 43.37 mmol) in tetrahydrofuran (60 g) was added dropwise. Drop 201031687 After the addition, the reaction temperature rose to 23 °C and the reaction was carried out. After confirming the completion of the reaction by HP (High Speed Liquid Chromatography), the reaction liquid was poured into distilled H water (1.2 L), and the precipitated solid was filtered, washed with water, and washed with 2-propanol (232 g) to obtain a dispersion. Compound [xvii] (yield: 27.69 g, yield: 95%). 'H-NMR (400 MHz &gt; DMSO-d6 &gt; δ ppm): 9.06 (1Η &gt; t) , 8.86 (2H, d) &gt; 3.44 ( 2H &gt; t ) , 2.79-2.66 (2H, m) The mixture containing the compound [xvii] (25.OOg, 3 7.1 mmol), iron powder (reduced iron, 12.42 g, 222.5 mmol) and ethyl acetate (22 5 g) was heated to 70 ° C under a nitrogen atmosphere. A 10% aqueous solution of ammonium chloride (5.9 5 g &gt; 111.3 mmol) was added. After confirming the completion of the reaction by HPLC, the solid was filtered with celite. After washing with 500 mL of ethyl acetate and distilled water, the aqueous layer was removed, and the organic layer was washed 3 times with distilled water (500 mL). Subsequently, the organic layer was dried over anhydrous magnesium sulfate, and after filtration, solvent was evaporated. The crude product of the obtained compound (DA-4) was washed with hexane (60 g), and filtered and dried to give Compound (DA-4) (yield: 19.5 g, yield: 85%). 'H-NMR (400MHz &gt; DMSO-d6 - &lt; 5 ppm) : 6.36 ( 2H,d) , 6.06 ( 1H,t) , 5.14 ( 4H,brs ) , 3.19 ( 2H,t), 2.64-2.5 1 ( 2H,m ). [Synthesis Example 8: Synthesis of Polyimine (PI-4)] -63- 201031687 In a nitrogen flow, a 3.5 mL 7-neck flask was charged with 3.583 7 g (8.73 mmol) of 2,2-bis (4- Aminophenoxyphenyl)propane (hereinafter referred to as BAPP), 0.1518 g (0.27 mmol) of DA-2, and after dissolving in 36.02 g of NMP, 2.6214 g (8.73 mmol) of 3,4-dicarboxyl was added. -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (hereinafter referred to as TDA) was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The solution of the obtained polyaminic acid was diluted to 8 mass% with NMP. To 100 g of this solution, 1 lg of acetic anhydride as a ruthenium iodide catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized by W-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (P 1-4 ). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (PI-4) were Mn = 14,300' Mw = 38,000, respectively. [Synthesis Example 9: Synthesis of Polyimine (PI-5)] 3.4728 g (8.46 mmol) of BAPP and 0·3 0 3 7 g were placed in a four-necked flask of 10 mL in a nitrogen stream. After DA-2 of (0 · 5 4 mm ο 1 ) was dissolved in 36.25 g of NMP, 2.6214 g ( 8.73 mmol) of TDA was added, and the mixture was stirred at 50 ° C for 24 hours to carry out polymerization. The resulting solution of polyamic acid was diluted to 8 mass% with NMP. To 30 g of this solution, ng was added as a ruthenium iodide catalyst acetic acid 201031687 anhydride, 5.2 g of pyridine, and reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be imidized by 90% or more by 1H-NMR. The powder of 2. lg was dissolved in a mixed solvent of 27.7 g of butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-5). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (P1-5) were Mn = 16,400 and Mw = 39.400, respectively. [Synthesis Example 10: Synthesis of Polyimine (PI-6)] 3.6206 g (8.82 mmol) of BAPP and 0.11 9 2 g (0.1 8) were placed in a four-necked flask of 10 mL in a nitrogen stream. After DA-3 of mmo 1 ), and dissolved in 36.05 g of NMP, 2.6214 g (8.73 mmol) of TDA was added, and the mixture was stirred at 5 ° C for 24 hours to carry out a polymerization reaction. The resulting solution of polyamic acid was diluted to 8 mass% with NMP. To the solution of 3 Og, llg of acetic anhydride as a ruthenium-imiding catalyst and 5.2 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain a polyimine solution. This solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be imidized by 90% or more by Η_NMR. This powder of 2.lg was dissolved in a mixed solvent of 27.7 g of 2r-butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-6). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (PI-6) were Mn = 20,200 and Mw = 51,400, respectively. -65-201031687 [Synthesis Example 11: Synthesis of polyimine (PI-7)] In a nitrogen flow, 3.9819 g (9.7 mmol) of B AP P, 0 · 1 8 was placed in a 100 mL four-necked flask. 4 2 g (0.3 mm ο 1 ) of DA-4, and after dissolving in 40.11 g of NMP, 2.9126 g (9.7 mmol) of TDA was added, and the mixture was stirred at 50 ° C for 24 hours to carry out a polymerization reaction. The solution of the obtained polyaminic acid was diluted to 8 mass% with NMP. To 100 g of this solution, 1 lg of acetic anhydride as a ruthenium amide catalyst and 5.2 g of pyridine were added, and reacted at 50 ° C for 3 hours to obtain a polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white polyimine powder. The polyimine powder was confirmed to be 90% or more imidized by W-NMR. 2.1 g of this powder was dissolved in a mixed solvent of 27.7 g of butyrolactone and 5.3 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-7). The number average molecular weight (??) and weight average molecular weight (Mw) of the obtained polyimine (PI-7) were Mn = 17,800 and Mw = 45,000, respectively. Synthesis Example 12: Synthesis of Polyimine Precursor (PI-8) In a four-necked flask of 10 mL, a BAPP, 0·1 8 4 2 was placed in a nitrogen cylinder. g (0.3 mm ο 1 ) of DA-4, and after dissolving in 34.39 g of NMP, add 1.9023 g (9.7 mmol) of CBDA, stir it at 23 ° C for 1 hour to carry out polymerization, and then dilute with NMP. Obtaining a 6 mass% solution of the polyamidiamine precursor (PI-8) 201031687 The number average molecular weight (?η) and the weight average molecular weight (Mw) of the obtained chitosan precursor (PI-8) are respectively Mn=14, 3 00, Mw = 3 2,100 [Synthesis Example 13: Synthesis of polyetherimine (PI-9) for blend] In a 200 mL four-necked flask, 4.86 g (0.045 mol) of a pair was placed in a nitrogen stream. - phenylenediamine, 1.74 g (0.005 mol) of 4-hexadecaneoxy-1,3-diaminobenzene, after dissolving in 122.5 g of NMP, adding 15.01 g (0.05 mol) of TDA, The polymerization was carried out by stirring at room temperature for 10 hours. The obtained polylysine solution was diluted with NMP to 8 mass%. To 50 g of this solution, 10.8 g of acetic anhydride as a ruthenium amide catalyst and 5.0 g of pyridine were added, and the mixture was reacted at 50 ° C for 3 hours to obtain Polyimine solution. The solution was poured into a large amount of methanol, and the resulting white precipitate was filtered off and dried to give a white pigment. The polyimine powder was confirmed to be 90% or more imidized by φ i-NMR. 4 g of this powder was dissolved in a mixed solvent of 52.67 g of r-butyrolactone and 1 g of dipropylene glycol monomethyl ether to obtain a 6 mass% solution of polyimine (PI-9). The number average molecular weight (?η) and weight average molecular weight (Mw) of the obtained polyimine (PI-9) were Mn = 18,000 Å Mw = 54,000, respectively. [Synthesis Example 1 4 ································································ The 6 wt% solution of the polyimine (PI-7)-67-201031687 was stirred at room temperature for 6 hours to obtain a composition a. [Synthesis Example 15: Preparation of Polymer Blend (Composition B)] 9 g of a 6 wt% solution of the polyimine (PI_9) prepared in Synthesis Example 13 and lg of the polyamide prepared in Synthesis Example 12 were mixed. A 6 wt% solution of the amine (PI-8) was stirred at room temperature for 6 hours to obtain a composition b. [Synthesis Example 16: Preparation of Polymer Blend (Composition C)] 8 g of a 6 wt% solution of the polyimine (PI-9) prepared in Synthesis Example 13 and 2 g of the polymerization prepared in Synthesis Example 12 were mixed. A 6 wt% solution of quinone imine (PI-8) was stirred at room temperature for 6 hours to obtain a composition C. The structural formula of the tetracarboxylic anhydride and the diamine compound synthesized or used in the examples is shown below. [Tetracarboxylic anhydride used in this example]

[Diamine used in this embodiment] -68- 201031687 [Chem. 39]

η2Ν^^ΝΗ DA-2 o=c-s-^-c6F13 Λ, 〇=c-s-^^-c8f17 o^-s-λ ώ· 17

DA-3 η2ν^^νη2 DA*4

&lt;Example 1&gt; Water contact angle change φ On a glass substrate (2.5 cm side length, thickness 〇. 7 mm) to which ΙΤΟ was attached, a syringe with an ο. 2 # m hole filter was used to add Synthesis Example 2 The prepared PI-1 solution was applied by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing at 21 (the hot plate of TC for 30 minutes to obtain a polyimide film having a film thickness of about 400 ηη. The water contact angle of the polyimide film is 0 (°). Two polyimide films are produced in the same order, and after irradiating ultraviolet rays with an irradiation amount of 20 J/cm 2 or 40 J/cm 2 , the water contact angle of the film is measured. 69-201031687 The results are shown in Table A. &lt;Example 2&gt; Change in water contact angle Three sheets of polyimine film were produced in the same manner as in Example 1 except that the solution of P1-2 prepared in Synthesis Example 3 was used. The film was irradiated with ultraviolet rays of 20 J/cm2 or a film irradiated with ultraviolet rays of 40 J/cm2, and the water contact angle of each film was measured by 0 (°). The results are shown in Table A. <Comparative Example 1 &gt; Water contact angle The film was prepared in the same manner as in Example 1 except that the solution of P1-3 prepared in Synthesis Example 4 was used, and each of the films was formed into an ultraviolet non-irradiation film or a film irradiated with ultraviolet rays of 40 Å/cm 2 . The water contact angle of the film was 0 (°). The results are shown in Table A. &lt;Example 3&gt; PGME contact angle change Three polyimine films were produced in the same manner as in Example 1, and each of them was an ultraviolet non-irradiated film, a film irradiated with ultraviolet rays 2J/cra2, or a film irradiated with ultraviolet rays of 6 J/cm 2 , and the contact angle of PGME of each film was measured 0 ( The results are shown in Table B. <Comparative Example 2> PGME contact angle change Two sheets of polyimine were produced in the same manner as in Example 70 except that the solution of PI_3 prepared in Synthesis Example 4 was used. Each of the films was an ultraviolet non-irradiated film or a film irradiated with ultraviolet rays of 6 J/cm 2 'The PGME contact angle of each film was 0 (°). The results are shown in Table B. <Example 4> PGME contact angle was changed with ITO On the glass substrate (2·5 cm side length, thickness 0.7 mm) φ, a solution of PI-4 prepared in Synthesis Example 8 was dropped using a syringe equipped with a 0.2 /zm hole filter, by spin coating After coating, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. The contact angle of the PGME solution of the polyimide film was measured as 0 (°) °. One piece of poly was produced in the same order. The yttrium imide film was irradiated with ultraviolet rays at an irradiation dose of 1 J/cm 2 , and the PGME contact angle of the film was measured as 0 (.). The results are not shown in Table C. <Example 5> PGME contact angle change except Synthesis Example 9 In the same manner as in Example 4, two polyimine films were produced in the same manner as in Example 4, and each of the films was irradiated with an ultraviolet ray unirradiated film and irradiated with ultraviolet rays of 1 J/cm 2 to measure the pgme contact angle of each film. The results are shown in Table C. 201031687 &lt;Example 6&gt; The PGME contact angle was changed except that PI-6 prepared by the synthesis example was used. In the same procedure as in Example 4, two polyimide films were produced, each of which was an ultraviolet non-irradiated film, and irradiated with ultraviolet rays U/. The film of cm2 was measured for the PGME contact angle 0 (.) of each film. The results are shown in Table C. &lt;Example 7&gt; The PGME contact angle was changed except that the composition A prepared in Synthesis Example 14 was used. In the same procedure as in Example 4, two polyimide films were produced, each of which was an ultraviolet non-irradiated film, and irradiated with ultraviolet rays. The film of cm2 was measured for the PGME contact angle ° (°) of each film. The result is not in Table C. &lt;Example 8&gt; The PGME contact angle change was carried out in the same manner as in Example 6 except that the composition C prepared in Synthesis Example 16 was used, and each of the two films was formed into an ultraviolet non-irradiation film and irradiated with ultraviolet rays. The film of cm2 was measured for the PGME contact angle ° (°) of each film. The results are shown in Table C. -72- 201031687 [Table 5] Table A Water contact angle measurement results using polymer ultraviolet rays not irradiated θ η UV irradiation after 0 (.) 20 J/cm 2 40 J/cm 2 Example 1 PI-1 98 72 15 Example 2 PI -2 95 43 7 Comparative Example 1 PI-3 88 - 81.8 [Table 6] Table B Measurement results of contact angle of PGME Using polymer ultraviolet rays not irradiated θ η UV irradiation period waste 0 (.) 2 J/cm 2 6 J/cm 2 Example 3 PI-1 20.1 9.8 10 Comparative Example 2 PI-3 17.7 - 19.4 ❹ [Table 7] Table C Measurement results of contact angle of PGME Irradiation with polymer ultraviolet rays D Irradiation 1 J/cm 2 Example 4 PI-4 17.3 8.4 Example 5 PI-5 31.7 18.3 Example 6 PI-6 25 16.7 Example 7 PI-7/PI-9 18.5 9.3 Example 8 PI-8/PI-9 27.1 16.9 As shown in Table A, Table B and Table C In the examples using the polyimine and the polyimide precursor prepared by the diamine having a thiol bond in the side chain, the P GME contact angle after the ultraviolet irradiation greatly changed. On the other hand, in the comparative examples 1 and 2 of the poly-imine precursor (PI-3) made of -73-201031687 which is made of a diamine having a thiol bond in a side chain, the contact angle of water or PGME The amount of change is small. This result is considered to be that if the polyimine precursor is a structure in which a side chain is a thiol ester group, a hydrophobic machine exists, that is, the thiol ester gene is irradiated by ultraviolet light to cause photodecomposition, and the side chain is hydrophobic. Part of the autonomous chain is cut and separated, thereby causing a large change in the hydrophilicity and hydrophobicity. &lt;Example 9&gt; Electrode patterning evaluation ^ On a glass substrate (2.5 cm side length, thickness 〇. 7 mm) with a crucible attached thereto, a syringe drop addition example with a 0.2 // m hole filter was used. A solution of 8 prepared PI-4 was applied by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. On the polyimide film, a portion of the polyimine was hydrophilized by irradiating ultraviolet rays 1 j/cm 2 through a reticle (line width 100 // m, pitch 1 〇〇 # m line and space). Subsequently, a silver fine particle dispersion was added dropwise to the ultraviolet irradiation portion, and baked at a temperature of 180 ° C for 60 minutes to form a silver electrode having a film thickness of 50 nm. A micrograph of this silver electrode is shown in Fig. 1. A film composed of PI-4 can form a silver electrode which becomes a target line width. &lt;Example 1&gt; Electrode patterning evaluation In addition to the composition A prepared in Synthesis Example 14, a film-forming polyimide film was formed in the same procedure as in Example 9 on the polyimide film. Through the -74-201031687 mask (line width 1 00 &quot; m, spacing 1 00 # m line and space), UV U/cm2 is irradiated to make one part of the polyimine hydrophile. Subsequently, a silver fine particle dispersion was added dropwise to the ultraviolet irradiation portion, and baked at a temperature of 180 ° C for 60 minutes to form a silver electrode having a film thickness of 50 nm. A micrograph of this silver electrode is shown in Fig. 2. The film composed of the composition A can form a silver electrode which becomes a target line width. φ &lt;Comparative Example 3 &gt; Electrode patterning evaluation

A polyimide film was formed in the same order as in Example 1 except that PI-3 prepared in Synthesis Example 4 was used, and the firing temperature was 210 ° C. The polyimide film was passed through the mask ( The line width l〇〇/zm, the line of 100/im pitch and space) is irradiated with ultraviolet rays of 1 J/cm2. Subsequently, the silver fine particle dispersion liquid was added in a small amount. However, since the ultraviolet irradiation portion was not hydrophilized, the electrode could not be formed. The results of Example 9 to Example 10 and Comparative Example 3 are shown in the table by P1-4 having a thiol ester bond. And the film composed of the composition A, the hydrophilicity of the ultraviolet irradiation amount of 1 i / cm 2 has been sufficiently changed, and the silver electrode of the "m line width" can be formed 'instead, by having no thiol ester bond In the film composed of the composition D, the hydrophilicity of the ultraviolet irradiation amount of 1 j/cm 2 was not sufficiently changed, and the electrode could not be formed. -75- 201031687

Table D Electric Cui Giant Formation Ability (U/cm2) Formation Using Polymer Electrode Example 9 PI-4 Possible Example 10 Composition A Possible Comparison Example 3 PI-3 Impossible &lt;Example 11&gt; Insulation is attached On a glass substrate of ITO (2.5 cm side length, thickness 0.7 mm), a solution of PI-1 prepared in Synthesis Example 2 was dropped by using a syringe equipped with a 〇.2#m-pore filter, by spin coating. Coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to evaporate the organic solvent, followed by firing on a hot plate at 210 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 nm. Then, in order to obtain good contact between the ITO electrode and the probe of the measuring device, one part of the polyimide film is peeled off to expose the ITO, and then the diameter is laminated on the polyimide film and the ITO by using a vacuum evaporation device. 1.0 mm, aluminum electrode with a film thickness of 100 nm. The vacuum vapor deposition conditions at this time were set to room temperature, the degree of vacuum was 3 x 10 3 Pa or less, and the aluminum vapor deposition rate was 3 3 nm / sec or less. A sample for evaluation of current-voltage characteristics of the polyimide film was prepared by forming an electrode above and below the polyimide film. The prepared sample was immediately subjected to a current-voltage characteristic in a nitrogen atmosphere. The measured voltage is set to rise from 0V every 2V to 90V. At this time, the specific dielectric ratio of the polyimide film was 3.37, and the leakage current density was 3×1 (T1() A/cm 2 . Further, the electric field insulation of the polyimide film at 2 MV/cm was not destroyed. 201031687 Fig. 3 The measurement results of the current-voltage characteristics in a nitrogen atmosphere are shown. Next, the same sample as above was allowed to stand in the atmosphere (25 degrees, humidity 45%) for 15 hours, and then the current-voltage characteristics were measured. The measurement voltage was set to 0 V per 2 V. The temperature rises to 90 V. At this time, the sample leakage current density is 1.8 x 1 Ο * 7 A / cm 2 0 Figure 4 shows the measurement results of the current-voltage characteristics in the atmosphere. φ &lt;Example 12&gt; Insulation except polyimine film A sample for current-voltage characteristic evaluation was produced in the same manner as in Example 1 except that the firing temperature was changed to 23 ° C. The specific dielectric constant of the polyimide film at this time was 3.14, and the leak current density was 1. Οχ l(T1()A/cni2. Further, the electric field insulation of the polyimide film at 2 MV/cm is not destroyed.

Then, the same sample as above was allowed to stand for 15 hours in the atmosphere (25 degrees, humidity 45%), and the current-voltage characteristics were measured. The measured voltage is set to rise from φ 0 V every 2 V to 90 V. The sample leakage current density at this time was 1. 8 X 1 O'8 A/cm 2 ° Fig. 3 shows the results of measurement of current-voltage characteristics in a nitrogen atmosphere, and Fig. 4 shows the results of measurement of current-voltage characteristics in the atmosphere. &lt;Example 13&gt; Insulation on a ITO-attached glass substrate (2.5 cm side length, thickness: 0.7 mm) was applied by using a syringe attached with a 0.2 // m hole filter to add PI prepared in Synthesis Example 8. The solution of 4 was applied by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in an atmosphere at -77-201031687 to volatilize the organic solvent. Then, it was baked at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 400 nm. . Then, in order to obtain good contact between the ITO electrode and the probe of the measuring device, one part of the polyimide film is cut out to expose the ITO, and then the diameter is laminated on the polyimide film and the ITO by using a vacuum evaporation device. 1.0 mm aluminum electrode with a film thickness of 100 nm. The vacuum vapor deposition conditions at this time were set to room temperature, a vacuum degree of 3×l (T3 Pa or less, and an aluminum vapor deposition rate of 0.3 nm/sec or less. By forming an electrode above and below the polyimide film, a polyimide film was produced. Sample for evaluation of current-voltage characteristics. The prepared sample was allowed to stand at 23 ° C ± 3 ° C and humidity 45% ± 5% for 15 hours, and then the current-voltage characteristics were measured. The measured voltage was set to 0 V per 2 V. It rises to 100 V. The leakage current density of this sample at lMV/cm is 々^xlO — HA/cm 2 . Further, the polyimide film is still unbroken until 2 MV/cm. Figure 5 shows the results of current-voltage characteristics measurement. &lt;Example 14&gt; Insulation A sample for current-voltage characteristic evaluation was produced in the same order as in Example 13 except that the composition A prepared in Synthesis Example 14 was used. The leakage current density of this sample at 1 MV/cm was 1.7 x 1 (T1()A/cm2. Further, the polyimide film was not destroyed until 2 MV/cm. Fig. 5 shows the results of current-voltage characteristics measurement. &lt;Example 15&gt; Insulation-78-201031687 The composition B prepared in Example 15 was the same as in Example 13 except that the firing temperature was 2 3 0 °C. The sample for current-electrical evaluation was sequentially prepared. The leakage current density of this sample at lMV/cm was 1.2×1 (T. Further, the polyimide film was not destroyed until 2 MV/cm. Figure 5 shows the measurement of current-voltage characteristics. Results: φ &lt;Example 16&gt; Insulation A sample for current-electrical evaluation was produced in the same manner as in Example 13 except that the composition C prepared in Synthesis Example 16 was used and the baking temperature was 23 °C. The leakage current density of /cm is 3.4x10^. Further, the polyimide film is not destroyed until 2MV/cm. Figure 5 shows the results of current-voltage characteristics measurement. As shown in Figure 3, it consists of PI-1. The film is different in the atmosphere of nitrogen gas (Example 1 1 and Example 12). As shown in Fig. 4, the film composed of PI-1 is susceptible to water leakage current density visible in the atmosphere. In addition to the nitrogen atmosphere, the water is used as a method for forming an underlayer film for the image without any problem. Example 1 1 and Example 1 2). Further, as shown in Fig. 5, PI-4 and composition A to C The film is an excellent insulating film (Examples 13 to 16). That is, the formed image forming method of the present invention is used. The film is a layer film having sufficient insulating properties for forming an underlayer film for forming an image. The degree is set to a pressure characteristic of 0 A/cm 2 and the pressure characteristic is °A/cm 2 . As a shape-79 - 201031687 &lt;Example 17: Transistor characteristics&gt; On a glass substrate (2.5 cm side length, thickness 0.7 mm) with a Cr electrode, a needle with a 〇.2/im hole filter was used. A solution of PI-4 prepared in Synthesis Example 8 was added dropwise to the solution by spin coating. Subsequently, it was heat-treated at 80 ° C for 5 minutes in the atmosphere to volatilize the organic solvent, followed by firing on a hot plate at 180 ° C for 30 minutes to obtain a polyimide film having a film thickness of about 450 nm. The polyimide film was irradiated with ultraviolet rays of 2 J/cm 2 through a mask to hydrophilize a part of the polyimide. Then, a silver fine particle dispersion liquid was added dropwise to the ultraviolet irradiation portion, and fired in a heating plate of 180 ° for 60 minutes to form a source and a drain electrode having a film thickness of 5 Onm. On the silver electrode, pentacene (manufactured by Aldrich) was formed into a film of 70 nm by vacuum evaporation. The vapor deposition rate of pentacene was set to 0.05 nm/second. The electrical characteristics of the organic thin film transistor obtained above were evaluated by measuring the change in the source current with respect to the gate voltage. In detail, the source and drain voltages (VD) are set to -80V, and the gate voltage (VG) varies from +20V to -80V in 2V steps, and the voltage is maintained for 1 second before the current is fully stabilized.値 is recorded as a measurement of the buckling current, and this operation is repeated 5 times. Further, the measurement was carried out in a nitrogen atmosphere using a semiconductor parameter analyzer HP415 6C (manufactured by AGILENT Technologies). Generally, the drain current Id in a saturated state can be expressed by the following equation. That is, the mobility A of the organic semiconductor can be obtained by taking the absolute square root of the drain current Id as the vertical axis and the slope of the pattern when the gate voltage Vg is plotted on the horizontal axis -80-201031687.

Id = WC β (Vg-Vt) 2/2L In the above formula, W is the channel width of the transistor, L is the channel length of the transistor, C is the electrostatic capacitance of the gate insulating film, and VT is the threshold voltage of the transistor. #为移动度. The transistor W made in this example has W = 2 mm, L = 1 Ο 0 /z m » C = 6.4 nF/cm 2 . The mobility of pentacene / / based on this formula, the average is 5 x 10 2 cm2 / Vs. Further, the threshold 値 voltage is from -18V to -20V, and the ratio of the ON state to the OFF state (on/off ratio) is 1〇6. Further, repeating the measurement and not transmitting the transfer characteristic (Transfer Characteristics) offset to obtain the stability characteristics (Fig. 6). The film obtained from P 1-4 is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor. &lt;Example 18: Transistor characteristics&gt; An organic transistor was produced in the same manner as in Example 17 except that the composition A prepared in Synthesis Example 14 was used. The transistor W made in this embodiment has W = 2 m m, L = 1 0 0 / / m, and C = 6 · 5 n F / c m 2 . The mobility of pentacene / / based on this formula, the average is 5x l (T2cm2 / Vs. Again, the threshold 値 voltage from -19V to -21 V, the ratio of open state to off state (on / off ratio) is 1 〇ό grade. Repeated measurement did not reveal the characteristic shift to obtain the stability characteristics (Fig. 7). It is shown that the film obtained from the composition 不仅 is excellent not only as an electrode forming film but also as a gate insulating film for an organic transistor. -81 - 201031687 &lt;Example 19: Transistor characteristics&gt; An organic transistor was produced in the same manner as in Example 17 except that the amount of ultraviolet irradiation was set to 1 J/cm 2 . 2mm, L = 1 00 /zm &gt; C = 6.4nF/cm2. The mobility of pentacene / / based on this formula, the average is 3x l (T2cm2 / VS. Again, the threshold 値 voltage from -16V to -20V The ratio of the on state to the off state (on/off ratio) is 1 06. Further, repeated measurement is performed to show that the characteristic shift is obtained to obtain the stability characteristic (Fig. 8). The film obtained from the composition A is not only used as the film. The electrode formation film is excellent and is also excellent as a gate insulating film for an organic transistor. [Industry may be advantageous According to the present invention, the underlayer film for forming an image can be used to shorten the necessary exposure time for changing the hydrophilicity and hydrophobicity, and it is expected to reduce the manufacturing cost when forming a patterned layer of a functional material such as an electrode. By irradiating the polarized light UV, it is also possible to impart anisotropy to the film obtained from the polyimine precursor and the polyimide, that is, an alignment treatment film which is a functional material such as a liquid crystal or a semiconductor, and In the same manner as in the case of forming an underlayer film for an image, it is expected to shorten the manufacturing time. [Schematic Description of the Drawing] Fig. 1 is a photomicrograph showing a silver electrode on PI_4 produced in Example 9 (silver electrode line width is 100//m) -82 - 201031687 Fig. 2 is a photomicrograph showing the silver electrode on the composition A produced in Example 10 (silver electrode line width is 1 〇〇A m ). Fig. 3 is a view showing the polyimine precursor A graph of current-voltage characteristics of a polyimide film obtained by firing (PI-1) in a nitrogen atmosphere (Example 11 and Example 1 2). Figure 4 shows a polyimide precursor (PI). -1) the polyimine film obtained by firing Fig. 5 is a graph showing the current-voltage characteristics of the polyimide film produced in Examples 13 to 16 in the atmosphere. Fig. 6 is a view showing the transmission characteristics of an organic transistor in which an electrode obtained by irradiating a film of PI-4 is irradiated with 2 J/cm 2 of ultraviolet rays and processing an electrode (Example 17). Fig. 7 is a view showing irradiation of a film obtained from the composition a. Figure 2 shows the transmission characteristics of an organic transistor with 2J/cm2 ultraviolet rays and processed electrodes (Example 18) ° ❹ Figure 8 shows the transmission of an organic transistor which irradiates the film obtained from PI-4 with 丨j/cm2 ultraviolet rays and processes the electrode. Figure of the characteristics (Example 19). -83-

Claims (1)

201031687 VII. Patent application scope: ι_ An underlayer film for forming an image, which is characterized by comprising a polyimine precursor having a repetitive structure represented by the following formula (η) or a polycondensation of the polyimine precursor Yttrium imine: [Chemical 1] R1OOC COOR2 ~N—C—A—C—N—B I II II I HO OH (1 ) (wherein A represents a tetravalent organic group, B represents a divalent structure represented by the following formula (2) or (3), and I^ and R2 each independently represent a hydrogen atom or a monovalent organic group, and η represents a natural number); [Chemical 2] Ο u S—C 一Χ—Υ-Ζ (3) (R)t (X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -0-, -COO-, -OCO-, -CONH-, - CH20-, -CH2COO- or -CH2CH2COO-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom, and R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon atom. The alkyl group 't of 1 to 3 represents an integer of 〇 to 3). 2. The underlayer film for forming an image is characterized in that it contains a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine containing a formula represented by the following formula (7) The polyamido-84-201031687 amine precursor obtained by the reaction of an amine component, or the polyazide obtained by dehydrating and ring-closing the polyimine precursor (6) h2n-b-nh2 (7) Wherein A represents a divalent structure represented by a tetravalent organic group: B represents a formula (2) or a formula (3) [Chemical 4] X—YZ (3) (wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and γ represents a single bond, -Ο-, -COO-, -OCO-, -CONH-, - CH20-, -ch2coo- or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which may be substituted by a fluorine atom. R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon atom. An alkyl group of 1 to 3, and t represents an integer of 0 to 3)]. 3. The underlayer film for forming an image according to the first or second aspect of the patent application, wherein Z of the formula (2) or the formula (3) represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which is substituted by a fluorine atom of any hydrogen atom. 4. The underlayer film for forming an image according to any one of claims 1 to 3, wherein A represents a tetravalent organic group having an aliphatic ring or an aliphatic group only -85-201031687. 5. The lower layer film for forming an image according to any one of claims 1 to 4, wherein B represents a divalent structure represented by the formula (2). 6. The image forming the image according to any one of claims 1 to 5, wherein X and Y represent a single bond. An organic transistor characterized by comprising the underlayer film for forming an image according to any one of claims 1 to 6. 8. A diamine compound represented by the following formula (14) or the following formula (15) [Chemical 5] (wherein X represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -Ο-, -COO-, -OCO-, -CONH-, -CH2〇-, -CH2COO -or- CH2CH2COO-'Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms substituted by a fluorine atom of any hydrogen atom. R each independently represents a fluorine atom, an alkoxy group having 1 to 3 carbon atoms or a carbon atom number of 1 To an alkyl group of 3, t represents an integer from 〇 to 3). A polyimine which is characterized by containing a polyimine precursor of a repeating unit represented by the following formula (Ο) or by dehydrating a ring of the polyimine precursor, -86- (1) 201031687 6] R1OOC /COOR2 N—C—A—C—N—B· I II II I HO OH n (wherein A represents a tetravalent organic group, and B represents a divalent structure represented by the following formula (2a) or (3a); , R1, R2 independently represent a hydrogen atom or a monovalent organic group, η represents a natural number); [Chemical 7] ❿ 〇 = CS - XYZ SC - ~ 0 ~ ~ (23) (R) t (R), 〇 II S-CX—Y_Z K (3a) (R)t (wherein x represents a single bond or a divalent aromatic group having 6 to 20 carbon atoms, and Y represents a single bond, -Ο-, -COO-, -OCO -, -CONH-, -CH2〇-, -ch2coo- or -ch2ch2coo-, Z represents an aliphatic hydrocarbon group having 3 to 26 carbon atoms which is substituted by a fluorine atom of any hydrogen atom, and R each independently represents a fluorine atom, An alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents an integer of 0 to 3. 10. A formation film lower layer coating liquid comprising a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (6) and a diamine represented by the following formula (7) The polyimine precursor obtained by the reaction of the diamine component, or the polyimine obtained by dehydrating and ring-closing the polyimine precursor: -87- 201031687 [Chem. 8] Ο Ο Ο Ο Η2Ν-Β-ΝΗ2 (7) Ο (6) (wherein Α represents a tetravalent organic group, and Β represents a divalent structure represented by formula (2) or formula (3): [Chemical 9] 〇=c —s —X—Y~z Ό&quot; (2, (R)t !? 10 SCX 一Υ一ζ _Λ_ Κ (3) (R)t R1, R2 independently represent a hydrogen atom or a monovalent organic group, X represents A single bond or a divalent aromatic group of 6 to 20 carbon atoms 'Y represents a single bond, -0-, -COO-, -OCO-, -CONH-, -CH20-, -CH2COO- or -CH2CH2COO-, Z The aliphatic hydrocarbon group which represents 3 to 26 carbon atoms which may be substituted by a fluorine atom 'R independently represents a fluorine atom, a methoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and t represents 0 to An integer of 3). 11. The image forming method of the underlayer film coating liquid according to claim 10, wherein Z of the formula (2) or the formula (3) represents an arbitrary hydrogen atom substituted with a fluorine atom and has 3 to 26 carbon atoms. The aliphatic hydrocarbon group of the image forming method according to the first or the eleventh aspect of the patent application, further comprising a soluble polyimine having a ruthenium iodide ratio of 80% or more. Forming an underlying film, characterized by Patent Application No. -88 - 201031687 The formation of the underlayer film coating liquid is obtained by the formation of the image of the 10th to 12th. 14. An organic transistor characterized by having the lower layer of the image forming of the patent claims 10th to 13th. A film obtained by firing a film coating liquid. -89 -