JP2012136476A - Diimide compound, inkjet ink and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound suitable as a curing component of an inkjet ink capable of forming a polyimide film having less warping amount.SOLUTION: This diimide compound (A) is expressed by formula (1) [wherein, X is a 2C-100C tetravalent organic group; Ys are each independently a 1C-100C divalent organic group; and Zs are each independently a 1C-100C divalent organic group].

Description

  The present invention relates to a novel diimide compound, for example, an ink-jet ink used for forming an insulating film in the production of electronic components, a polyimide film obtained from the ink and a method for producing the same, a film substrate or a silicon wafer substrate, and an electronic component .

  Polyimide is widely used in the field of electronic communication because it has excellent heat resistance and electrical insulation (see, for example, Patent Documents 1 to 3). In the case of using polyimide as a desired pattern film, conventionally, a method of forming a pattern using etching or photosensitive polyimide has been generally used. However, the formation of the pattern requires a large amount of chemicals such as a photoresist, a developer, an etching solution, a stripping solution, and a complicated process. Therefore, in recent years, a method of forming a desired polyimide pattern film by inkjet has been studied.

  Various ink-jet inks have been proposed (see, for example, Patent Documents 4 to 5), but in order to eject and print as ink-jet inks, various parameters such as ink viscosity and solvent boiling point must be optimized. Must not.

  Regarding the viscosity, generally, it is required to have a low viscosity of about 1 to 50 mPa · s at the discharge temperature (the temperature of the ink at the time of discharge). In particular, in the case of piezo-type ink jet printing, since the discharge pressure of the piezoelectric element is small, if the viscosity increases, ink cannot be discharged in some cases.

  The boiling point of the solvent at 1 atm is preferably 100 to 300 ° C, and more preferably 150 to 250 ° C. If the boiling point is too low, the solvent in the ink at the nozzle portion of the printer head will evaporate particularly when the ink is heated and ejected. As a result, the viscosity of the ink changes, and the ink cannot be ejected or the ink components may solidify. On the other hand, if the boiling point is too high, the drying of the ink after printing is too slow and the printing pattern may be deteriorated.

  The polyimide-based inkjet ink contains polyimide or a polyamic acid that becomes a polyimide by heat treatment. As an inkjet ink containing a polyamic acid, a resin composition containing a solvent having a viscosity and a polymer concentration set in a specific range and a boiling point and a surface tension in a specific range has been proposed (see, for example, Patent Document 6). ). However, in general, in inkjet inks containing polyamic acid, warpage of the substrate and the polyimide film often becomes a problem due to curing shrinkage during firing.

  On the other hand, since polyimide or polyamic acid has a high molecular weight, it is necessary to increase the solvent ratio to reduce the content of polyamic acid in the ink in order to prepare an ink having an optimum viscosity as an ink-jet ink. However, this reduces the thickness of the polyimide film obtained by one ink jetting.

  Depending on the use of the polyimide film, a thickness of 10 μm or more may be required. In this case, a film having this thickness can be formed by overcoating with an ink jet. However, there is a problem in that the number of times of overcoating increases, that is, the number of steps of forming the insulating film increases because the thickness of the polyimide film obtained by one ink jetting is reduced.

JP 2000-039714 A JP 2003-238683 A JP 2004-094118 A JP 2003-213165 A JP 2006-131730 A JP 2005-187596 A

  An object of the present invention is to provide a novel compound suitable as a curable component of an inkjet ink capable of forming a polyimide film with a small amount of warpage. Further, the present invention is an ink containing the curable component, wherein (1) parameters such as viscosity are optimized for inkjet and a solvent that does not reduce the durability of the inkjet head can be used, and (2) 1 It is an object of the present invention to provide an ink capable of forming a polyimide film having a relatively large film thickness (2 μm or more) by jetting once, and a use of the ink.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using an ink jet ink containing a diimide compound (A) having a specific structure and the compound (A) and a solvent (B), thereby completing the present invention.

That is, the present invention is as follows.
[1] A diimide compound (A) represented by the formula (1).

［式（１）中、Ｘは炭素数２〜１００の四価の有機基であり、複数あるＹはそれぞれ独立に炭素数１〜１００の二価の有機基であり、複数あるＺはそれぞれ独立に炭素数１〜１００の二価の有機基である。］
［２］式（１）中、複数あるＹがそれぞれ独立に式（１−１）で表され、複数あるＺがそれぞれ独立に式（１−２）で表される、前記［１］に記載のジイミド化合物（Ａ）。

[In the formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms, a plurality of Y are each independently a divalent organic group having 1 to 100 carbon atoms, and a plurality of Z are each independent. And a divalent organic group having 1 to 100 carbon atoms. ]
[2] In Formula [1], in Formula (1), a plurality of Y are each independently represented by Formula (1-1), and a plurality of Z are each independently represented by Formula (1-2). The diimide compound (A).

［式（１−１）中、ｍは１〜１１の整数であり；ｍが１のときＲ¹は水素、炭素数１〜３０のアルキルまたは炭素数６〜１０のアリールであり、前記アルキルにおける任意の水素は、ヒドロキシル基、ヒドロキシフェニル基、チオール基、インドール基またはイミダゾール基で置き換えられてもよく、前記アルキルにおける任意の−ＣＨ₂−は−Ｓ−で置き換えられてもよく；ｍが２〜１１の整数のときＲ¹は水素である。］

[In the formula (1-1), m is an integer of 1 to 11; when m is 1, R ¹ is hydrogen, alkyl having 1 to 30 carbons or aryl having 6 to 10 carbons; Any hydrogen may be replaced with a hydroxyl group, a hydroxyphenyl group, a thiol group, an indole group or an imidazole group, and any —CH ₂ — in the alkyl may be replaced with —S—; When it is an integer of ˜11, R ¹ is hydrogen. ]

［式（１−２）中、Ｒ²は炭素数２〜１１の直鎖状アルキレンであり、ｎは０〜１０の整数である。］
［３］式（ａ１）で表されるテトラカルボン酸二無水物（ａ１）と、式（ａ２）で表されるアミノ酸（ａ２）と、式（ａ３）で表されるアルコール（ａ３）とを反応させて得られる、前記［１］または［２］に記載のジイミド化合物（Ａ）。

Wherein (1-2), R ² is a linear alkylene of 2 to 11 carbon atoms, n represents an integer of 0. ]
[3] A tetracarboxylic dianhydride (a1) represented by the formula (a1), an amino acid (a2) represented by the formula (a2), and an alcohol (a3) represented by the formula (a3). The diimide compound (A) according to the above [1] or [2] obtained by reacting.

［式（ａ１）中、Ｘは炭素数２〜１００の四価の有機基であり；式（ａ２）中、Ｙは炭素数１〜１００の二価の有機基であり；式（ａ３）中、Ｚは炭素数１〜１００の二価の有機基である。］
［４］アミノ酸（ａ２）が、式（ａ２−１）で表されるアミノ酸であり、アルコール（ａ３）が、式（ａ３−１）で表されるアルコールである、前記［３］に記載のジイミド化合物（Ａ）。

[In formula (a1), X is a tetravalent organic group having 2 to 100 carbon atoms; in formula (a2), Y is a divalent organic group having 1 to 100 carbon atoms; in formula (a3) , Z is a divalent organic group having 1 to 100 carbon atoms. ]
[4] The amino acid (a2) is an amino acid represented by the formula (a2-1), and the alcohol (a3) is an alcohol represented by the formula (a3-1). Diimide compound (A).

［式（ａ２−１）中、ｍは１〜１１の整数であり；ｍが１のときＲ¹は水素、炭素数１〜３０のアルキルまたは炭素数６〜１０のアリールであり、前記アルキルにおける任意の水素は、ヒドロキシル基、ヒドロキシフェニル基、チオール基、インドール基またはイミダゾール基で置き換えられてもよく、前記アルキルにおける任意の−ＣＨ₂−は−Ｓ−で置き換えられてもよく；ｍが２〜１１の整数のときＲ¹は水素である。］

[In the formula (a2-1), m is an integer of 1 to 11; when m is 1, R ¹ is hydrogen, alkyl having 1 to 30 carbons or aryl having 6 to 10 carbons; Any hydrogen may be replaced with a hydroxyl group, a hydroxyphenyl group, a thiol group, an indole group or an imidazole group, and any —CH ₂ — in the alkyl may be replaced with —S—; When the integer is ˜11, R ¹ is hydrogen. ]

［式（ａ３−１）中、Ｒ²は炭素数２〜１１の直鎖状アルキレンであり、ｎは０〜１０の整数である。］

[In Formula (a3-1), R ² is a linear alkylene having 2 to 11 carbon atoms, and n is an integer of 0 to 10. ]

[5] Tetracarboxylic dianhydride (a1) is pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone Tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 , 3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic acid Dianhydride 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride , Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,3-dihydro-1, 3-dioxo-5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] di-4,1-phenylene ester, 2,2-bis (4-hydroxyphenyl) Propane dibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,3-dihydro 1,3-dioxo-5-isobenzofurancarboxylic acid oxydi-4,1-phenylene ester, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxotetrahydrofuran-3-yl) ) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Bicyclohexyltetracarboxylic dianhydride, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride and 5- (2,5-dioxotetrahydrofuryl) -3- One or more selected from the group consisting of methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and the amino acid (a2) is glycine, alanine, β-alanine, phenyla One or more selected from the group consisting of nin, valine, leucine, isoleucine, cysteine, methionine, serine, threonine, tyrosine, tryptophan, histidine, 4-aminobutyric acid, 6-aminohexanoic acid and 12-aminolauric acid, The diimide compound (A) according to the above [3] or [4], wherein the alcohol (a3) is at least one selected from the group consisting of ethylene glycol monovinyl ether, diethylene glycol monovinyl ether and tetramethylene glycol monovinyl ether.

[6] An inkjet ink comprising the diimide compound (A) according to any one of [1] to [5] and a solvent (B).
[7] The inkjet ink according to [6], wherein the content of the diimide compound (A) is 5 to 95% by weight based on the total amount of the ink.
[8] The inkjet ink according to [6] or [7], wherein the viscosity at the inkjet discharge temperature is 1 to 50 mPa · s.
[9] Further, polyamic acid, imidized polymer of polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol, polyoxyethylene, polymerizable monomer, alkenyl substitution [6] to [8] including at least one selected from the group consisting of a nadiimide compound, a silicon amic acid compound, an epoxy resin, a surfactant, an antistatic agent, a coupling agent, an epoxy curing agent and a polymerization initiator. The inkjet ink according to any one of the above.

[10] The polyamic acid or imidized polymer thereof obtained by using at least a tetracarboxylic dianhydride and a diamine, and the polyamic acid or imidized polymer thereof having a structural unit represented by the following formula: [9] The inkjet ink according to [9].

［式中、Ｘは炭素数２〜１００の四価の有機基であり、Ｙは炭素数１〜１００の二価の有機基である。］
［１１］前記［６］〜［１０］のいずれか１項に記載のインクジェット用インクから得られるポリイミド膜。
［１２］前記［６］〜［１０］のいずれか１項に記載のインクジェット用インクをインクジェット塗布方法によって基板上に塗布して塗膜を形成した後、前記塗膜を硬化処理して得られるポリイミド膜。
［１３］前記［６］〜［１０］のいずれか１項に記載のインクジェット用インクをインクジェット塗布方法によって基板上に塗布して塗膜を形成する工程、および前記塗膜を硬化処理する工程を含む、ポリイミド膜の製造方法。
［１４］フィルムと、前記フィルム上に形成された前記［１１］または［１２］に記載のポリイミド膜とを有するフィルム基板。
［１５］前記［１４］に記載のフィルム基板を有する電子部品。
［１６］シリコンウエハーと、前記シリコンウエハー上に形成された前記［１１］または［１２］に記載のポリイミド膜とを有するシリコンウエハー基板。
［１７］前記［１６］に記載のシリコンウエハー基板を有する電子部品。

[Wherein, X is a tetravalent organic group having 2 to 100 carbon atoms, and Y is a divalent organic group having 1 to 100 carbon atoms. ]
[11] A polyimide film obtained from the inkjet ink according to any one of [6] to [10].
[12] Obtained by applying the inkjet ink according to any one of [6] to [10] onto a substrate by an inkjet coating method to form a coating film, and then curing the coating film. Polyimide film.
[13] A step of applying the inkjet ink according to any one of [6] to [10] onto a substrate by an inkjet application method to form a coating film, and a step of curing the coating film. A method for producing a polyimide film.
[14] A film substrate having a film and the polyimide film according to [11] or [12] formed on the film.
[15] An electronic component having the film substrate according to [14].
[16] A silicon wafer substrate having a silicon wafer and the polyimide film according to [11] or [12] formed on the silicon wafer.
[17] An electronic component having the silicon wafer substrate according to [16].

  ADVANTAGE OF THE INVENTION According to this invention, the novel compound suitable as a sclerosing | hardenable component of the inkjet ink which can form a polyimide film with little curvature amount can be provided. According to the invention, the ink includes the curable component, and (1) an ink in which a parameter such as viscosity is optimized for inkjet and a solvent that does not decrease the durability of the inkjet head can be used, and (2 ) It is possible to provide an ink capable of forming a polyimide film having a relatively large film thickness (2 μm or more) by one jetting, and a use of the ink.

  Hereinafter, each structure of the diimide compound of the present invention and a production method thereof, an inkjet ink, a polyimide film obtained from the ink and a production method thereof, a film substrate or a silicon wafer substrate, and an electronic component will be described.

1 Diimide compound (A)
The diimide compound (A) of the present invention is represented by the formula (1).

  In formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms, a plurality of Y are each independently a divalent organic group having 1 to 100 carbon atoms, and a plurality of Z are each independently A divalent organic group having 1 to 100 carbon atoms.

X is preferably a residue of tetracarboxylic dianhydride represented by the formula (a1) described later. The residue of tetracarboxylic dianhydride means X in the formula (a1) described later.
Y is preferably a divalent group represented by the formula (1-1).

In the formula (1-1), m is an integer of 1 to 11, preferably 1 or an integer of 2 to 6; when m is 1, R ¹ is hydrogen, alkyl having 1 to 30 carbons or 6 to 6 carbons. And any hydrogen in the alkyl may be replaced by a hydroxyl group, a hydroxyphenyl group, a thiol group, an indole group or an imidazole group, and any —CH ₂ — in the alkyl is —S—. May be substituted; when m is an integer from 2 to 11, R ¹ is hydrogen.

  The alkyl may be linear or branched. Examples of the alkyl include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, isobutyl, t-butyl and the like. The number of carbon atoms in the alkyl is preferably 1-8, more preferably 1-4. Examples of the aryl include phenyl, benzyl, tolyl, xylyl, naphthyl and the like.

  Examples of the alkyl substituted with the hydroxyl group include groups in which at least one hydrogen of the alkyl is substituted with a hydroxyl group (—OH), and specifically, hydroxymethyl, hydroxyethyl, s-hydroxybutyl. Etc.

Examples of the alkyl substituted with the hydroxyphenyl group include a group in which at least one hydrogen of the alkyl is substituted with a hydroxyphenyl group (—C ₆ H ₅ (OH)). And hydroxybenzyl.

  Examples of the alkyl substituted with the thiol group include a group in which at least one hydrogen of the alkyl is substituted with a thiol group (—SH), and specific examples include 1-mercaptomethyl.

  Examples of the alkyl substituted with -S- include a group in which at least one methylene of the alkyl is substituted with -S-, specifically, methylthioethyl and the like.

Examples of the alkyl substituted with the indole group or the imidazole group include groups in which at least one hydrogen of the alkyl is replaced with an indole group (indole ring) or an imidazole group (imidazole ring). 3-indolyl) methyl, (5-imidazolyl) methyl and the like.
Z is preferably a divalent group represented by the formula (1-2).

In Formula (1-2), R ² is a linear alkylene having 2 to 11 carbon atoms, and the alkylene preferably has 2 to 4 carbon atoms; n is an integer of 0 to 10, preferably It is an integer of 0-2.

Since the diimide compound (A) of the present invention has already been imidized and has a terminal structure of —O—CH═CH ₂ , it can be cured by using this as a curable component of an inkjet ink, for example. Curing shrinkage at the time of processing becomes small, and thus warpage of the obtained polyimide film can be reduced. Further, since the diimide compound (A) of the present invention has a relatively low molecular weight, for example, when used as a curable component of an ink jet ink, the viscosity of the ink can be optimized and the concentration of the compound can be increased. it can. When the diimide compound (A) is polymerized and cured, the electrical characteristics (heat resistance, electrical insulation, mechanical characteristics derived from the imide) of the obtained polyimide film are ensured. Since the diimide compound (A) has already been imidized, the storage stability at room temperature storage is excellent as compared with the amic acid type compound.

2 Production Method of Diimide Compound (A) The diimide compound (A) of the present invention is, for example, a tetracarboxylic dianhydride represented by the formula (a1) (hereinafter also referred to as “tetracarboxylic dianhydride (a1)”). ), An amino acid represented by formula (a2) (hereinafter also referred to as “amino acid (a2)”), and an alcohol represented by formula (a3) (hereinafter also referred to as “alcohol (a3)”). It can be obtained by reaction.

  In the formula (a1), X is a tetravalent organic group having 2 to 100 carbon atoms; in the formula (a2), Y is a divalent organic group having 1 to 100 carbon atoms; in the formula (a3), Z is a divalent organic group having 1 to 100 carbon atoms.

2.1 Tetracarboxylic dianhydride (a1)
The tetracarboxylic dianhydride (a1) is represented by the above formula (a1), specifically pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2, 2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride Anhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethane Tracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methyl Cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1 , 3-Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] di-4,1-phenylene ester, 2,2- Bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid oxydi-4,1-phenylene ester, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5- Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-di Oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and the like. 4,4 ′-[(isopropylidene) bis (p-phenyleneoxy)] diphthalic dianhydride, ethylenediaminetetraacetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro- Examples thereof include 1-naphthalene succinic dianhydride and compounds represented by the following formulas a1-1 to a1-56.

  Among the specific examples of tetracarboxylic dianhydride (a1), pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Diphenylsulfone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2- [Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride P-phenylenebis (trimellitic acid monoester anhydride), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 ′ It is preferable to use a hexyl dianhydride bicyclo.

  Further, depending on the application, high transparency is required. In such a case, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, Cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3 It is particularly preferred to use 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride.

2.2 Amino acid (a2)
The amino acid (a2) is represented by the above formula (a2). The amino acid (a2) is preferably an amino acid represented by the formula (a2-1) from the viewpoint of solubility of the resulting compound in the solvent (B).

In the formula (a2-1), m is an integer of 1 to 11, preferably 1 or an integer of 2 to 6; when m is 1, R ¹ is hydrogen, alkyl having 1 to 30 carbons or carbon number. Any hydrogen in the alkyl may be replaced by a hydroxyl group, a hydroxyphenyl group, a thiol group, an indole group or an imidazole group, and any —CH ₂ — in the alkyl is —S -May be replaced by R; when m is an integer from 2 to 11, R ¹ is hydrogen. Preferred groups and examples of R ¹ in formula (a2-1) are the same as the groups and examples described in formula (1-1) above.

  Specific examples of the amino acid (a2) include glycine, alanine, β-alanine, phenylalanine, valine, leucine, isoleucine, cysteine, methionine, serine, threonine, tyrosine, tryptophan, histidine, 4-aminobutyric acid, 6-aminohexane. Examples include acid and 12-aminolauric acid.

2.3 Alcohol (a3)
The alcohol (a3) is represented by the above formula (a3). The alcohol (a3) is preferably an alcohol represented by the formula (a3-1) from the viewpoint of reducing warpage of the obtained polyimide film.

In Formula (a3-1), R ² is a linear alkylene having 2 to 11 carbon atoms, and the alkylene preferably has 2 to 4 carbon atoms; n is an integer of 0 to 10, preferably It is an integer of 0-2.

  Specific examples of the alcohol (a3) include ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and tetramethylene glycol monovinyl ether. Of these, ethylene glycol monovinyl ether is preferable.

2.4 Synthesis conditions for diimide compound (A) The diimide compound (A) can be obtained, for example, by reacting a tetracarboxylic dianhydride (a1), an amino acid (a2), and an alcohol (a3). . Specifically, the diimide compound (A) is obtained by imidizing a diamic acid compound synthesized using a tetracarboxylic dianhydride (a1) and an amino acid (a2), and the resulting diimide intermediate and alcohol (a3). ) And can be obtained.

<Synthesis of diamide acid compound>
The diamic acid compound can be synthesized under mild reaction conditions by mixing tetracarboxylic dianhydride (a1) and amino acid (a2). The mild reaction conditions are, for example, a temperature of 5 to 60 ° C. and a reaction time of 0.2 to 20 hours under normal pressure, preferably a temperature of 5 to 30 ° C. and a reaction time of 0.2 to 3 hours. Without any activation, the carboxyl group produced by ring opening by the reaction of the acid anhydride group of tetracarboxylic dianhydride (a1) is reacted. The activation of the carboxyl group is, for example, conversion to acid chloride.

  Under the above mild reaction conditions, the carboxyl group produced by the reaction of the acid anhydride group of tetracarboxylic dianhydride (a1) with the amino group of amino acid (a2) reacts with the amino group of amino acid (a2). Therefore, a diamide acid compound having a free carboxyl group can be obtained.

  In the synthesis of the diamic acid compound, the order of adding the reaction raw materials to the reaction system is not particularly limited. For example, (1) a method in which tetracarboxylic dianhydride (a1) and amino acid (a2) are simultaneously added to the reaction solvent, (2) after dissolving amino acid (a2) in the reaction solvent, tetracarboxylic acid is added to the reaction solvent. Any method such as a method of adding acid dianhydride (a1), (3) a method of adding amino acid (a2) to the reaction solvent after dissolving tetracarboxylic dianhydride (a1) in the reaction solvent, etc. Methods can also be used.

  The amount of tetracarboxylic dianhydride (a1) and amino acid (a2) used is 0.5 to 4.0 moles of amino acid (a2) per mole of tetracarboxylic dianhydride (a1). Is preferably used, more preferably 0.7 to 3.0 mol, and even more preferably 1.0 to 2.4 mol.

<Synthesis of diimide intermediate>
The diimide intermediate can be obtained by imidizing the diamide acid compound. Although imidation can be advanced by a thermal method or a chemical method using a dehydration catalyst and a dehydrating agent, it is preferable to proceed by a thermal method that can be used without performing a purification treatment.

  The imidization of the diamic acid compound is preferably advanced by a thermal method, specifically, heating under reflux. The reflux conditions vary depending on the reaction solvent to be used, but the temperature is usually 70 to 230 ° C., preferably 140 to 230 ° C., and the reaction time is usually 1.5 to 10 hours, preferably 2 to 4 hours. When the temperature is 70 ° C. or higher, a diimide compound (A) capable of forming a film is easily obtained. When the temperature is 140 ° C. or higher, imidization proceeds sufficiently and a diimide compound (A) capable of forming a stronger film is easily obtained. When the temperature is 230 ° C. or lower, it can be refluxed even when a reaction solvent having a relatively high boiling point is used. After heating to reflux, the reaction solvent, unreacted substances such as tetracarboxylic dianhydride (a1) and amino acid (a2), and water produced by the reaction are usually distilled off.

  Moreover, it may replace with said mild reaction conditions in the synthesis | combination of a diimide acid compound, and may obtain a diimide intermediate body by advancing the synthesis | combination and imidation of a diamide acid compound on the said reflux conditions.

<Synthesis of diimide compound (A)>
The diimide compound (A) can be obtained by reacting the diimide intermediate with the alcohol (a3). In the reaction, the carboxylic acid part of the diimide intermediate reacts with the alcohol part of the alcohol (a3).

  At this time, it is preferable to advance the reaction by activating the carboxylic acid portion of the diimide intermediate. For example, a method in which a carboxylic acid portion of a diimide intermediate is converted to an acid chloride using thionyl chloride and the like, and then reacted with an alcohol (a3). A diimide intermediate and an alcohol (a3) using an amide condensing agent such as dicyclohexylcarbodiimide And a method of reacting with.

  The reaction conditions are, for example, a temperature of 0 to 80 ° C. and a reaction time of 0.2 to 30 hours in the presence of a base. Examples of the base include triethylamine, pyridine, 4- (dimethylamino) pyridine and the like.

  As preparation amount of alcohol (a3), it is preferable to use 2.0-10.0 mol of alcohol (a3) with respect to 1 mol of diimide intermediates, and it is more preferable to use 2.0-5.0 mol. More preferably, 2.0 to 3.0 mol is used.

<Reaction solvent>
When synthesizing the diimide compound (A), more specifically, when synthesizing the diamic acid compound, the diimide intermediate and the diimide compound (A), a reaction solvent can be used.

  The reaction solvent is ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl. Ethyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, triethylene glycol divinyl ether, tripropylene Glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, γ-butyrolactone, 4-methyl-2-pentanone, anisole, ethyl lactate, toluene, Methyl benzoate, ethyl benzoate, dichloromethane, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl- Examples include 2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone.

  Among these reaction solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, γ-butyrolactone, 4-methyl-2-pentanone, toluene, and dichloromethane are soluble. Is preferable.

  A reaction solvent may be used by 1 type and may be used in mixture of 2 or more types. In addition, other solvents than the above reaction solvent can be used by mixing with the reaction solvent.

  The reaction solvent is used in an amount of 100 parts by weight or more with respect to a total of 100 parts by weight of reaction raw materials such as tetracarboxylic dianhydride (a1), amino acid (a2) and alcohol (a3), from the viewpoint of allowing the reaction to proceed smoothly. It is preferable.

3 Inkjet ink The inkjet ink of the present invention contains the diimide compound (A) and the solvent (B). The ink may further contain another additive (C). The ink-jet ink of the present invention may be colored or colorless.

3.1 Diimide compound (A)
The diimide compound (A) and preferred embodiments thereof are as described above.
The content of the diimide compound (A) is preferably 5 to 95% by weight, more preferably 25 to 80% by weight, and particularly preferably 30 to 70% by weight with respect to the total amount of the ink. A higher concentration of the diimide compound (A) is preferable because the thickness of the polyimide film obtained from the ink increases, but on the other hand, the viscosity of the ink also tends to increase, so that the ink cannot be ejected by the ink jet printer. There is also. In the present invention, within the above concentration range, a polyimide film having a relatively large film thickness (for example, 2 μm or more) can be easily formed by one jetting, and the ink viscosity can be inkjet printed. It can be easily adjusted to the viscosity range.

3.2 Solvent (B)
The solvent (B) is not particularly limited as long as it can dissolve the diimide compound (A). In addition, even if the solvent alone does not dissolve the diimide compound (A), the mixed solvent is used as a solvent as long as the mixed solvent can dissolve the diimide compound (A) by mixing with another solvent. It can be used as (B).
The boiling point of the solvent (B) at 1 atm is usually 100 to 300 ° C, preferably 150 to 250 ° C.

  Examples of the solvent (B) include ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, Propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol Ethylene glycol dimethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, methyl 3-methoxypropionate, 3-ethoxy Ethyl lopionate, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, γ-butyrolactone, anisole, ethyl lactate, methyl benzoate, ethyl benzoate, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxy Silane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N, N-dimethylpropionamide, N, N, N ′, N′-tetramethylurine 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, Examples include 1-acetyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methyl-ε-caprolactam, and carbamic acid ester.

  Among the solvents (B), from the viewpoint of improving the durability of the inkjet head, ethyl lactate, ethylene glycol, propylene glycol, glycerin, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane , Methyltrimethoxy Silane, methyl triethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane are preferred.

  Of the solvents exemplified above, when the durability of the ink jet head is a problem, it is also preferable to reduce the use of an amide solvent. In such a case, the content of the amide solvent is preferably 0 to 20% by weight with respect to the total amount of the solvent (B), and is 0% by weight, that is, the solvent (B) is a non-amide solvent. It is more preferable that On the other hand, when the polymer compound described later is contained in the ink, from the viewpoint of solubility, the content of the amide solvent is set to more than 0% by weight and not more than 20% by weight with respect to the total amount of the solvent (B). Also good.

  Examples of the amide solvent include N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N -Methylpropionamide, N, N-dimethylpropionamide, N, N, N ', N'-tetramethylurea, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl 2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1-acetyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methyl- ε-caprolactam and carbamic acid ester are exemplified.

As described above, a reaction solvent is usually used for the synthesis of the diimide compound (A). For this reason, when the said reaction solvent remains when the synthesis | combination of a diimide compound (A) is completed, the reaction solvent can also be used as a solvent (B).
A solvent (B) may be used by 1 type, and may mix and use 2 or more types.

  The content of the solvent (B) is preferably 1 to 95% by weight, more preferably 1 to 70% by weight, and particularly preferably 1 to 60% by weight with respect to the total amount of the ink. If the content of the solvent (B) is not less than the lower limit, the viscosity of the ink jet ink does not become too high, and the jetting characteristics are good. If content of a solvent (B) is below the said upper limit, the polyimide film which can be formed by one jetting will not become thin too much.

3.3 Additive (C)
Examples of additives (C) include polyamic acid, imidized polymer of polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol, polyoxyethylene, polymerization Monomer, alkenyl-substituted nadiimide compound, silicon amide acid compound, epoxy resin, surfactant, antistatic agent, coupling agent, epoxy curing agent, and polymerization initiator. Additives (C) further include pH adjusters, rust inhibitors, antiseptics, antifungal agents, antioxidants, anti-reduction agents, evaporation accelerators, chelating agents, water-soluble polymers, pigments, dyes, and the like. Can be mentioned. An additive (C) may be used by 1 type, and 2 or more types may be mixed and used for it.

3.3.1 Weight average molecular weight and concentration of polymer compound Polyamic acid, imidized polymer of polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol and poly In an additive selected from oxyethylene (hereinafter also referred to as “polymer compound”), its weight average molecular weight (Mw) is usually 1,000 to 10,000, preferably 1,000 to 7,500, Preferably it is 1,000-5,000, Most preferably, it is 1,000-2,000.

  A polymer compound having Mw equal to or higher than the above lower limit is not chemically evaporated by heat treatment and is chemically and mechanically stable. Since the polymer compound having Mw equal to or less than the above upper limit has a particularly high solubility in the solvent (B), the concentration of the polymer compound in the ink can be increased, and thus the coating obtained by applying the ink is used. The flexibility and heat resistance of the film can be improved. That is, a polymer compound having Mw in the above range is preferable as a component contained in an inkjet ink.

  The Mw of the polymer compound can be measured by a gel permeation chromatography (GPC) method. Specifically, the polymer compound is diluted with tetrahydrofuran (THF) or the like so as to have a concentration of about 1% by weight, and as a GPC apparatus, JASCO GULIVER 1500 (intelligent differential refractometer RI-) manufactured by JASCO Corporation. 1530), and the column G4000HXL, G3000HXL, G2500HXL, and G2000HXL manufactured by Tosoh Co., Ltd. connected in this order as a column, column temperature: 40 ° C., flow rate: 1.0 ml / min, Mw can be obtained by performing measurement by GPC method using THF as a developing agent and converting to polystyrene.

  The concentration of the polymer compound in the inkjet ink of the present invention is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. When the concentration is within such a range, good characteristics as an insulating film may be imparted.

3.3.2 Polyamic acid or imidized polymer thereof Polyamic acid or imidized polymer thereof is obtained using at least tetracarboxylic dianhydride (e1) and diamine (e2), and has the formula (e3) A polyamic acid having a structural unit represented by the formula (I) or an imidized polymer thereof is preferable.

  In formula (e3), X is a tetravalent organic group having 2 to 100 carbon atoms, and Y is a divalent organic group having 1 to 100 carbon atoms.

  Examples of the tetracarboxylic dianhydride (e1) include the compounds exemplified as the tetracarboxylic dianhydride (a1). Examples of the diamine (e2) include a diamine represented by the formula (e2-1) (hereinafter also referred to as “diamine (e2-1)”).

式（ｅ２−１）中、Ｙは炭素数１〜１００の二価の有機基である。

In formula (e2-1), Y is a C1-C100 bivalent organic group.

  Examples of the diamine (e2) include m-xylylenediamine, p-xylylenediamine, and compounds represented by formulas (I) to (VII).

In formula (I), A ¹ is — (CH ₂ ) _m —, where m is an integer of 1-6.
In the formulas (III), (V) and (VII), A ² represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO. _{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - (CH 2) n -, - O- (CH 2) n -O- or -S- (CH _{2) n} -S -Where n is an integer from 1-6.

In formulas (VI) and (VII), two A ³ groups are each independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF _{3). 2} ) or alkylene having 1 to 3 carbon atoms.

In the above formulas (I) to (VII), at least one hydrogen which the cyclohexane ring or the benzene ring has may be replaced by —F or —CH ₃ .

  Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-3).

  Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-2).

  Examples of the compound represented by the formula (III) include compounds represented by the formulas (III-1) to (III-3).

  Examples of the compound represented by the formula (IV) include compounds represented by the formulas (IV-1) to (IV-5).

  Examples of the compound represented by the formula (V) include compounds represented by the formulas (V-1) to (V-30).

  Examples of the compound represented by the formula (VI) include compounds represented by the formulas (VI-1) to (VI-6).

  Examples of the compound represented by the formula (VII) include compounds represented by the formulas (VII-1) to (VII-11).

Among the above specific examples of the compounds represented by the formulas (I) to (VII), the formulas (IV-1) to (IV-5), the formulas (V-1) to (V-12), the formula ( V-26), formula (V-27), formula (VI-1), formula (VI-2), formula (VI-6) and compounds represented by formulas (VII-1) to (VII-5) And more preferably compounds represented by formulas (V-1) to (V-12).
Among the diamines (e2), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, P-xylylenediamine, 2,2′-diaminodiphenylpropane, benzidine, and 1,1-bis [4- (4-aminobenzyl) phenyl] methane are preferred.

  Examples of the diamine (e2) further include a compound represented by the formula (VIII).

In the formula (VIII), A ⁴ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _p —, where p is 1 to 6 Is an integer. R ⁶ is a group having a steroid skeleton or a group having at least one ring structure selected from the group consisting of a cyclohexane ring and a benzene ring. When the positional relationship between the two amino groups bonded to the benzene ring is para, R ⁶ may be alkyl having 1 to 30 carbon atoms, and when the positional relationship is meta, R 6 ⁶ alkyl having 1 to 10 carbon atoms, or _{-F,, -CH 3, -OCH 3} , -OCH 2 F, or may be phenyl optionally replaced by -OCHF ₂ or -OCF _3.

The alkyl having 1 to 30 carbon atoms and the alkyl having 1 to 10 carbon atoms in R ⁶ may be linear or branched. In these alkyls, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, and any —CH _{3 —} May be replaced by —CH ₂ F, —CHF ₂ or —CF ₃ .

In formula (VIII), the two amino groups are bonded to the phenyl ring carbon, but the bonding position relationship between the two amino groups is preferably the meta position or the para position. Further, the two amino groups may be bonded to the 3-position and 5-position, or the 2-position and 5-position, respectively, when the bonding position of “R ⁶ -A ⁴ —” to the benzene ring is 1-position. preferable.
Examples of the compound represented by the formula (VIII) include compounds represented by the formulas (VIII-1) to (VIII-11).

In the formulas (VIII-1), (VIII-2), (VIII-7) and (VIII-8), R ⁷ is an organic group having 1 to 30 carbon atoms, alkyl having 3 to 12 carbons or carbon number It is preferably 3 to 12 alkoxy, more preferably alkyl having 5 to 12 carbons or alkoxy having 5 to 12 carbons.

In formulas (VIII-3) to (VIII-6) and (VIII-9) to (VIII-11), R ⁸ is an organic group having 1 to 30 carbon atoms, alkyl having 1 to 10 carbon atoms or carbon number It is preferably 1 to 10 alkoxy, more preferably alkyl having 3 to 10 carbons or alkoxy having 3 to 10 carbons.

  Examples of the compound represented by the formula (VIII) further include compounds represented by the formulas (VIII-12) to (VIII-17).

In formulas (VIII-12) to (VIII-15), R ⁹ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 4 to 16 carbon atoms, and alkyl having 6 to 16 carbon atoms. More preferably.

In Formula (VIII-16) and Formula (VIII-17), R ¹⁰ is an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and an alkyl group having 8 to 20 carbon atoms. More preferably it is.

  Examples of the compound represented by the formula (VIII) further include compounds represented by the formulas (VIII-18) to (VIII-38).

Formulas (VIII-18), (VIII-19), (VIII-22), (VIII-24), (VIII-25), (VIII-28), (VIII-30), (VIII-31), ( In (VIII-36) and (VIII-37), R ¹¹ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons, and having 3 carbon atoms. More preferably, it is -12 alkyl or C3-C12 alkoxy.

Formulas (VIII-20), (VIII-21), (VIII-23), (VIII-26), (VIII-27), (VIII-29), (VIII-32) to (VIII-35) and ( VIII-38) in, R ¹² is hydrogen, -F, alkyl having 1 to 12 carbon atoms, having 1 to 12 carbon atoms alkoxy, -CN, -OCH ₂ F, a -OCHF ₂ or -OCF _3, carbon atoms It is preferably 3 to 12 alkyl or C 3 to C 12 alkoxy.

In formulas (VIII-33) and (VIII-34), A ⁵ is alkylene having 1 to 12 carbons.
Examples of the compound represented by the formula (VIII) further include compounds represented by the formulas (VIII-39) to (VIII-48).

  Of the compounds represented by the formula (VIII), compounds represented by the formula (VIII-1) to the formula (VIII-11) are preferable, and the formula (VIII-2), the formula (VIII-4), the formula (VIII) The compounds represented by -5) and formula (VIII-6) are more preferred.

  In the present invention, examples of the diamine (e2) further include compounds represented by formulas (IX) to (X).

In formulas (IX) and (X), R ¹³ is hydrogen or —CH ₃ , and two R ^{14 s} are each independently hydrogen, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons, Two A ⁶ groups are each independently a single bond, —C (═O) — or —CH ₂ —.

In the formula (X), R ¹⁵ and R ¹⁶ are each independently hydrogen, alkyl having 1 to 20 carbons or phenyl.

In formula (IX), “NH ₂ —Ph—A ⁶ —O—” (—Ph— represents phenylene) bonded to the B ring of the steroid nucleus is bonded to the 6-position carbon of the steroid nucleus. It is preferable. Further, the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to the bonding position of A ^{6 to} the phenyl ring.

In formula (X), two “NH ₂ — (R ¹⁶ —) Ph—A ⁶ —O—” (—Ph— represents phenylene) are each bonded to a phenyl ring carbon. the steroid nucleus and the ring when ^{_{"NH 2 - - (R 16)}} Ph-a 6 -O- " is considered to be bonded, the steroid nucleus and ^{_{"NH 2 - (R 16 -)}} Ph-a 6 -O The positional relationship with “−” is preferably the meta position or the para position. The two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to A ⁶ .

  Examples of the compound represented by the formula (IX) include compounds represented by the formulas (IX-1) to (IX-4).

  Examples of the compound represented by the formula (X) include compounds represented by the formulas (X-1) to (X-8).

  Examples of the diamine (e2) further include compounds represented by formulas (XI) and (XII).

In the formula (XI), R ¹⁷ is hydrogen or alkyl having 1 to 20 carbon atoms, and in the alkyl, arbitrary —CH ₂ — is replaced by —O—, —CH═CH— or —C≡C—. Two A ^{7 s} that are present independently are —O— or alkylene having 1 to 6 carbon atoms, A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms, and ring T is 1 , 4-phenylene or 1,4-cyclohexylene, and h is 0 or 1.

In the formula (XII), R ¹⁸ is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable. R ¹⁹ is hydrogen or alkyl having 1 to 30 carbons, and among these, alkyl having 1 to 10 carbons is preferable. Two A ^{9 s} are each independently —O— or alkylene having 1 to 6 carbons.

In formula (XI), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta or para position with respect to A ⁷ . In formula (XII), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta or para position with respect to A ⁹ .

  Examples of the compound represented by the formula (XI) include 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4. -Methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane and the like (XI- The compounds represented by 1) to (XI-9) are mentioned.

In formulas (XI-1) to (XI-3), R ²⁰ is hydrogen or alkyl having 1 to 20 carbons.
In formulas (XI-4) to (XI-9), R ²¹ is hydrogen or alkyl having 1 to 20 carbons, and preferably hydrogen or alkyl having 1 to 10 carbons.

  Examples of the compound represented by the formula (XII) include compounds represented by the formulas (XII-1) to (XII-3).

In formulas (XII-1) to (XII-3), R ²² is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable, and R ²³ is hydrogen or having 1 to 30 carbons. Among these, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.

  Further, examples of diamine (e2) include diethylene glycol bis (3-aminopropyl) ether, 1,2-bis (2-aminoethoxy) ethane, 1,4-butanediol bis (3-aminopropyl) ether, 3, 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-bis (4-aminophenoxy) biphenyl, 1,6-bis (4- ((4-aminophenyl) methyl) phenyl) hexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1 , 4-bis (3-aminopropyl) piperazine, N, N′-bis (3-aminopropyl) ethylenediamine, 1,4-bis (aminomethyl) cyclohexane, Mention may also be made of 1,3-bis (aminomethyl) cyclohexane and neopentylglycol bis (4-aminophenyl) ether.

  As described above, as the diamine (e2), for example, compounds represented by the above formulas (I) to (XII) can be used, but compounds having two amino groups other than these compounds can also be used. Can do. For example, a naphthalene-type diamine having a naphthalene structure, a fluorene-type diamine having a fluorene structure, or a siloxane-type diamine having a siloxane bond is used alone or mixed with the compounds mentioned as compounds having two other amino groups. be able to.

  The siloxane-based diamine is not particularly limited, but a compound represented by the formula (XIII) can be preferably used in the present invention.

In the formula (XIII), R ³ and R ⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁵ is methylene or phenylene optionally substituted with alkyl having 1 to 10 carbon atoms, Two x are each independently an integer of 1 to 6, and y is an integer of 1 to 70. Depending on the use of the polyamic acid or its imidized polymer, high transparency is required. In such a case, y is particularly preferably an integer of 1 to 15. A plurality of R ³ , R ⁴ and R ⁵ may be the same or different from each other.

Examples of the diamine (e2) further include compounds represented by formulas (11) to (18). In formulas (11) to (18), R ²⁴ and R ²⁵ are each independently alkyl having 3 to 20 carbon atoms.

  The diamine (e2) is not limited to the compounds described in the present specification, and various other forms of diamine can be used as long as the object of the present invention is achieved.

3.3.3 Polymerizable monomer The inkjet ink of the present invention may further contain a polymerizable monomer other than the diimide compound (A). Use of a polymerizable monomer is preferable from the viewpoints of thickening and flexibility of the coating film. Examples of the polymerizable monomer include a monofunctional polymerizable monomer having hydroxyl, a monofunctional polymerizable monomer having no hydroxyl, a bifunctional (meth) acrylate, and a trifunctional or higher polyfunctional (meth) acrylate.

  Examples of the monofunctional polymerizable monomer having hydroxyl include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,4-cyclohexanedimethanol mono (meta). ) Hydroxyl-containing monofunctional (meth) acrylates such as acrylates.

Examples of the monofunctional polymerizable monomer having no hydroxyl include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth). Acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (Meth) acrylate, glycerol mono (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, Zyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl Oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, p-vinylphenyl-3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3 -(Meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (3-ethyl-3-oxetanyl) Methyl (meth) acrylate, styrene, methylstyrene, Chlormethylstyrene, vinyltoluene, N-cyclohexylmaleimide, N-phenylmaleimide, (meth) acrylamide, N-acryloylmorpholine, polystyrene macromonomer, polymethylmethacrylate macromonomer, (meth) acrylic acid, crotonic acid, α-chloroacrylic Acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono And [2- (meth) acryloyloxyethyl], cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl].

  Examples of the bifunctional (meth) acrylate include bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, and pentaerythritol diacrylate. Acrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-bis (acryloyloxy) decane, 1,4-cyclohexanedimethanol Diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, trimethylolpropane diacrylate Acrylate, dipentaerythritol diacrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and epichlorohydrin modified tri Methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified tri (meth) acrylate phosphate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.
A polymerizable monomer may be used by 1 type, and may mix and use 2 or more types.

  The polymerizable monomer concentration in the inkjet ink of the present invention is preferably 0 to 60% by weight, more preferably 0 to 50% by weight. When a polymerizable monomer is used, the lower limit of the concentration is about 10% by weight. When the concentration is within such a range, the heat resistance of the coating film formed from the ink jet ink of the present invention is improved.

3.3.4 Alkenyl-Substituted Nadiimide Compound The alkenyl-substituted nadiimide compound is not particularly limited as long as it has at least one alkenyl-substituted nadiimide structure in the molecule. For example, it is described in International Publication No. 2008/059986. And an alkenyl-substituted nadiimide compound represented by the formula (II-1).

In formula (II-1), R ¹⁴ and R ¹⁵ are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 12 carbons. Aryl or benzyl, n is an integer from 1 to 2,
When n = 1, R ¹⁶ is hydrogen, alkyl having 1 to 12 carbons, hydroxyalkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,-{( C _q H _2q ) O _t (C _r H _2r O) _u C _s H _2s X} (where q, r and s are each independently an integer of 2 to 6, t is an integer of 0 or 1, u is A polyoxyalkylene alkyl represented by an integer of 1 to 30, X is hydrogen or a hydroxyl group,-(R) _a -C ₆ H ₄ -R ¹⁷ (where a is an integer of 0 or 1, R is A group represented by alkylene having 1 to 4 carbon atoms, R ¹⁷ represents hydrogen or alkyl having 1 to 4 carbon atoms, and —C ₆ H ₄ —TC ₆ H ₅ (where T is —CH ₂ -, -C (CH ₃ ) _2- , -CO-, -S- or SO _2- ), or an aromatic ring of these groups. 1 to 3 hydrogens are replaced by hydroxyl groups,
When n = 2, R ¹⁶ is alkylene represented by —C _p H _2p — (wherein p is an integer of 2 to 20), cycloalkylene having 5 to 8 carbon atoms, — {(C _q H _{2q O) t (C r H} 2r O) u C s H 2s} - ( wherein, q, r, s are each independently an integer of 2 to 6, t is an integer of 0 or 1, u is from 1 to 30 polyoxyalkylene represented by the integer which is), arylene having 6 to 12 carbon _{^{atoms, - (R 17) a -C}} 6 H 4 -R 18 - ( wherein, a is an integer of 0 or 1, R ¹⁷ And R ¹⁸ are each independently a group having 1 to 4 carbon atoms, —C ₆ H ₄ —TC ₆ H ₄ — (wherein T is —CH ₂ —, —C ( CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O—, —S—, —SO ₂ —), or On the aromatic ring of these groups 1-3 hydrogen formation is a group which is replaced by a hydroxyl group.

Among the alkenyl-substituted nadiimide compounds represented by the formula (II-1),
R ¹⁴ and R ¹⁵ are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons or benzyl,
n is 2,
Alkylene in which R ¹⁶ is represented by —C _p H _2p — (wherein p is an integer of 2 to 10), — (R ¹⁷ ) _a —C ₆ H ₄ —R ¹⁸ — (where a Is an integer of 0 or 1, R ¹⁷ and R ¹⁸ are each independently alkylene having 1 to 4 carbon atoms, or —C ₆ H ₄ —TC ₆ H ₄ — (wherein T represents —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O—, —S— or —SO ₂ —. Is a group represented by
Alkenyl substituted nadiimide compounds are preferred.

Among the alkenyl-substituted nadiimide compounds represented by the formula (II-1), R ¹⁴ and R ¹⁵ are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, and R ¹⁶ is — (CH _{2) 6} -, a group represented by the group or the following formula represented by the following formula (II-2) (II- 3), an alkenyl-substituted nadiimide compounds are particularly preferred.

  The alkenyl-substituted nadiimide compound concentration in the inkjet ink of the present invention is preferably 0 to 40% by weight, more preferably 0 to 20% by weight. When the concentration is within such a range, good characteristics as an insulating film may be imparted.

3.3.5 Silicon amic acid compound The silicon amic acid compound is not particularly limited as long as it is a silicon amic acid compound having an amidic acid structure in the molecule. For example, it is described in International Publication No. 2008/123190 pamphlet. And silicon amide acid represented by formula (III) or silicon amide acid represented by formula (IV) having at least two amide acid structures in the molecule.

  Among the silicon amide acids represented by the formula (III), silicon amide acids represented by the following formula (III-1), (III-2) or (III-3) are preferable. Among the silicon amide acids represented by the formula (IV), silicon amide acids represented by the following formulas (IV-1), (IV-2), (IV-3) or (IV-4) are preferable.

In the formula (III), R ¹ , R ² and R ³ are each independently hydrogen, halogen or a monovalent organic group having 1 to 100 carbon atoms, and X is a tetravalent organic group having 1 to 100 carbon atoms. Y is an organic group having 1 to 20 carbon atoms.

In the formula (III-1), (III-2) or (III-3), R ¹ , R ² and R ³ are each independently hydrogen, halogen or a monovalent organic group having 1 to 100 carbon atoms, At least one of R ¹ , R ² and R ³ includes an alkoxy group having 1 to 20 carbon atoms, and a is an integer of 1 to 20.

In formula (IV), R ¹ , R ² and R ³ are each independently hydrogen, halogen or a monovalent organic group having 1 to 100 carbon atoms, and Y ′ is a trivalent organic group having 1 to 20 carbon atoms. And X ′ is a divalent organic group having 1 to 100 carbon atoms.

In formulas (IV-1), (IV-2), (IV-3) and (IV-4), R ¹ , R ² and R ³ are each independently hydrogen, halogen or monovalent from 1 to 100 carbon atoms. And at least one of R ¹ , R ² and R ³ contains an alkoxy group having 1 to 20 carbon atoms, and a is an integer of 1 to 20. R in the formula (IV-3) is a monovalent organic group having 2 to 30 carbon atoms. R in the formula (IV-4) is hydrogen or alkyl having 1 to 20 carbons.

  The silicon amic acid compound concentration in the inkjet ink of the present invention is preferably 0 to 30% by weight, more preferably 0 to 20% by weight. When the concentration is within such a range, good characteristics as an insulating film may be imparted.

3.3.6 Epoxy resin The epoxy resin is not particularly limited as long as it is a compound having an oxirane ring or an oxetane ring, but a compound having two or more oxirane rings is preferred. However, the compound classified into the above-mentioned polymerizable monomer is excluded.

  Examples of the epoxy resin include bisphenol A type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis ( N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, a compound having alkoxysilyl and an oxirane ring, a polymer of a monomer having an oxirane ring And a copolymer of a monomer having an oxirane ring and another monomer.

  Examples of the monomer having an oxirane ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

  Other monomers that copolymerize with monomers having an oxirane ring include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloro Examples include methylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

  Preferable specific examples of a polymer of a monomer having an oxirane ring and a copolymer of a monomer having an oxirane ring and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer Polymer, n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate copolymer Is mentioned. It is preferable to include these epoxy resins in the inkjet ink because the heat resistance of the polyimide film formed from the inkjet ink is improved.

  Among epoxy resins, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′ A compound represented by -tetraglycidyl-4,4'-diaminodiphenylmethane is preferred.

Examples of commercially available epoxy resins include trade names “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 190P”, “Epicoat 191P”, and trade names “ "Epicoat 1004", "Epicoat 1256" (currently available as jER (trade name) of Mitsubishi Chemical Corporation), trade name "Araldite CY177", trade name "Araldite CY184" (manufactured by Ciba Geigy Japan) ), Trade names “Celoxide 2021P”, “Celoxide 3000”, “EHPE-3150” (manufactured by Daicel Chemical Industries, Ltd.), and trade names “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.). Among these, the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “Techmore VG3101L”, and the trade name “Epicoat 828” are preferable because the flatness of the resulting polyimide film is particularly good.
An epoxy resin may be used by 1 type and may be used in mixture of 2 or more types.

  Examples of the epoxy resin further include compounds represented by formulas (I) to (VI). Among these, the compounds represented by the formulas (I), (IV) and (V) are preferable because the obtained polyimide film has particularly good flatness.

In the formula (V), R ^f , R ^g and R ^h are each independently hydrogen or an organic group having 1 to 30 carbon atoms, preferably hydrogen or alkoxy having 1 to 10 carbon atoms. Wherein (VI), R ^c is a tetravalent organic group having 2 to 100 carbon atoms, R ^d is a divalent organic group having 1 to 30 carbon atoms, R ^e is the formula (VII) ~ (IX ) Is a monovalent organic group selected from the group consisting of:

式（VII）中、Ｒⁱは水素または炭素数１〜３のアルキルである。

In formula (VII), R ⁱ is hydrogen or alkyl having 1 to 3 carbon atoms.

  The compound represented by the formula (VI) is obtained by, for example, reacting a tetracarboxylic dianhydride represented by the formula (VI-1) and a compound having a hydroxyl represented by the formula (VI-2) in a solvent. Can be obtained.

R ^c, R ^d and R ^e in the formula (VI-1) and (VI-2) is, R ^c in each formula (VI), it is synonymous with R ^d and R ^e. In the formula (VI-2), R ^d is a divalent organic group having 1 to 30 carbon atoms, for example, a linear or branched divalent organic group having 1 to 30 carbon atoms, A ring structure or oxygen may be contained, and examples of the ring structure include phenyl, cyclohexyl, naphthyl, cyclohexenyl, tricyclo [5.2.1.0 ^2,6 ] decanyl and the like.

Examples of the compound represented by the formula (VI) include a compound represented by the following formula (VI ′).

  The tetracarboxylic dianhydride represented by the formula (VI-1) is preferably a tetracarboxylic dianhydride (e1) that can be used for the synthesis of the above-described polyamic acid or imidized polymer thereof.

  It is preferable to use 1.9 to 2.1 mol of the compound having hydroxyl represented by formula (VI-2) with respect to 1 mol of tetracarboxylic dianhydride represented by formula (VI-1). It is more preferable to use 1.95 to 2.05 mol of the compound having hydroxyl represented by the formula (VI-2), and it is particularly preferable to use 2 mol of the compound having hydroxyl represented by the formula (VI-2). preferable. Two or more kinds of compounds having a hydroxyl group represented by the formula (VI-2) may be used in combination, but are preferably the same.

  The compound represented by the formula (VI) is, for example, a compound obtained by reacting a tetracarboxylic dianhydride represented by the formula (VI-1) with a compound having hydroxyl and a double bond. It can also be produced by oxidizing the double bond portion to an epoxy group.

  Although the solvent used in order to synthesize | combine the compound represented by Formula (VI) is not specifically limited, For example, the reaction solvent for synthesize | combining a diimide compound (A) is mentioned.

The solvent is preferably used in an amount of 50 parts by weight or more based on 100 parts by weight of the total reaction raw material of the compound represented by the formula (VI), from the viewpoint of allowing the reaction to proceed smoothly. The reaction temperature is preferably 80 ° C to 130 ° C, and the reaction time is preferably 2 to 8 hours. The order of adding the reaction raw materials to the reaction system is not particularly limited.
An epoxy resin may be used by 1 type and may be used in mixture of 2 or more types.

  The epoxy resin concentration in the inkjet ink of the present invention is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight. Within such a concentration range, the heat resistance, chemical resistance and flatness of the polyimide film formed from the ink jet ink of the present invention are improved.

3.3.7 Surfactant The surfactant can be used to improve the wettability, leveling, or coating property of the ink-jet ink of the present invention to the base substrate, and the ink-jet ink of the present invention. It is preferably used in an amount of 0.01 to 1% by weight in 100% by weight.

As the surfactant, for example, the trade names “Byk-300”, “Byk-306”, “Byk-335”, “Byk-310”, “ Silicone surfactants such as “Byk-341”, “Byk-344”, “Byk-370” (by BYK Chemie); trade names “Byk-354”, “ByK-358”, “Byk-361” Acrylic surfactants (made by Big Chemie Co., Ltd.) and the like; Fluorosurfactants such as trade names “DFX-18”, “Factent 250”, “Furgent 251” (made by Neos) It is done.
Surfactant may be used by 1 type and may be used in mixture of 2 or more types.

3.3.8 Antistatic Agent An antistatic agent can be used to prevent charging of the inkjet ink of the present invention, and is 0.01 to 1% by weight in 100% by weight of the inkjet ink of the present invention. Is preferably used in an amount of.

A known antistatic agent can be used as the antistatic agent. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; and quaternary ammonium salts.
An antistatic agent may be used by 1 type, and 2 or more types may be mixed and used for it.

3.3.9 Coupling Agent A known coupling agent can be used as the coupling agent, and it is preferably used in an amount of 0.01 to 3% by weight in 100% by weight of the inkjet ink of the present invention. .

  Examples of the coupling agent include a silane coupling agent. Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds.

Examples of trialkoxysilane compounds or dialkoxysilane compounds include γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, and γ-acryloylpropyl. Methyldiethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-aminopropyl Methyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxy Sisilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltri Methoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Examples include aminopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyltriethoxysilane. . Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are particularly preferable.
A coupling agent may be used by 1 type, and 2 or more types may be mixed and used for it.

3.3.10 Epoxy curing agent When using an epoxy resin or the like in the present invention, it is preferable to use an epoxy curing agent. As the epoxy curing agent, a known epoxy curing agent can be used, and it is preferably used in an amount of 0.2 to 5% by weight in 100% by weight of the inkjet ink of the present invention.

  Examples of the epoxy curing agent include organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, polycarboxylic acids, and polycarboxylic anhydrides.

More specifically, dicyandiamides such as dicyandiamide; organic acid dihydrazides such as adipic acid dihydrazide and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin; 2,4-diamino-6- [2′- Ethylimidazolyl- (1 ′)]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, imidazole derivatives such as 2-phenyl-4-methyl-5-hydroxymethylimidazole; phthalic anhydride, anhydrous tri Examples include merit acid and acid anhydrides such as 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride; trimellitic acid. Among these, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferable.
An epoxy hardening | curing agent may be used by 1 type, and 2 or more types may be mixed and used for it.

3.3.11 Polymerization initiator The polymerization initiator accelerates the polymerization of the polymerizable monomer when the vinyl group or additive of the diimide compound (A) is added during firing of the ink-jet ink of the present invention. Can be used for. The polymerization initiator is preferably used in an amount of 0.1 to 15% by weight in 100% by weight of the inkjet ink of the present invention.

  A known polymerization initiator can be used as the polymerization initiator. Specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 4 , 4′-azobis (4-cyanovaleric acid) and the like. A polymerization initiator may be used by 1 type and may be used in mixture of 2 or more types.

3.4 Method for Preparing Inkjet Ink The inkjet ink of the present invention can be prepared by uniformly mixing the diimide compound (A), the solvent (B), and, if necessary, the additive (C). it can. Moreover, the ink-jet ink of the present invention is prepared by using the reaction solution obtained at the time of synthesis of the diimide compound (A) as it is and uniformly mixing with the solvent (B) and the additive (C) as necessary. You can also

  The ink-jet ink of the present invention can optimize parameters such as viscosity, surface tension, and boiling point of the solvent for ink-jet printing, exhibits good ink-jet printability (eg, drawability, thick film formation), and stable storage Excellent in properties. Further, by using the ink, it is possible to form a polyimide film having good thermal, electrical, and mechanical characteristics and a small amount of warpage.

3.5 Characteristics of inkjet ink
3.5.1 Viscosity of inkjet ink The viscosity of the inkjet ink of the present invention at the temperature (ejection temperature) when ejected from the inkjet head is preferably 1 to 50 mPa · s, more preferably 5 to 30 mPa · s. More preferably, it is 5-20 mPa * s, Most preferably, it is 8-15 mPa * s. When the viscosity is in the above range, jetting accuracy by the ink jet coating method is improved. If the viscosity is less than or equal to the above upper limit value, poor inkjet discharge is unlikely to occur.
Since jetting is often performed at room temperature (25 ° C.), the viscosity of the inkjet ink of the present invention at 25 ° C. is preferably 1 to 50 mPa · s, more preferably 5 to 30 mPa · s, and still more preferably 5 to 5 mPa · s. 20 mPa · s. When the viscosity at 25 ° C. is in the above range, jetting accuracy by the ink jet coating method is improved. If the viscosity at 25 ° C. is less than or equal to the above upper limit value, inkjet discharge defects are unlikely to occur.

3.5.2 Surface tension of inkjet ink The surface tension of the inkjet ink of the present invention at 25 ° C. is preferably 20 to 45 mN / m, more preferably 20 to 40 mN / m. When the surface tension is in the above range, good droplets can be formed by jetting, and a meniscus can be formed.

3.5.3 Water Content of Inkjet Ink The water content in the inkjet ink of the present invention is preferably 10,000 wtppm or less, more preferably 5,000 wtppm or less. When the water content is in the above range, the inkjet ink has little change in viscosity and is excellent in storage stability.

4 Polyimide film The polyimide film of the present invention is obtained from the ink jet ink described above. For example, the ink of the present invention can be obtained by applying a coating film on a substrate by an inkjet coating method and then curing the coating film.

  When the coating film is printed in a pattern (eg, a line), a patterned polyimide film is formed. In the present specification, unless otherwise specified, the polyimide film includes a patterned polyimide film.

The inkjet ink of the present invention can contain the diimide compound (A) at a high concentration as described above. For this reason, in one ink jetting, the film thickness of the polyimide film of the present invention can be made larger than the film thickness of the polyimide film obtained from the conventional ink jet ink. The film thickness of the polyimide film of the present invention is usually 2 μm or more, preferably 2 to 10 μm.
The polyimide film of the present invention has, for example, high heat resistance and electrical insulation, has sufficient mechanical strength, has a small amount of warpage, and can improve the reliability and yield of electronic components.

5. Manufacturing Method of Polyimide Film The manufacturing method of the polyimide film of the present invention includes (1) a step of forming a coating film by applying the ink of the present invention on a substrate by an inkjet coating method (coating film forming step), and (2 ) Having a step of curing the coating film (a curing treatment step).

5.1 Coating Film Forming Process There are various types of ink jet coating methods depending on the ink ejection method. Examples of the discharge method include a piezoelectric element type, a bubble jet (registered trademark) type, a continuous injection type, and an electrostatic induction type.

  The ink of the present invention can be ejected by various methods by appropriately selecting the contained components, and according to the ink jet coating method, the ink of the present invention can be applied in a predetermined pattern. .

  A preferred ejection method when coating using the inkjet ink of the present invention is a piezoelectric element type. The piezoelectric element-type head includes a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite to the nozzles, and ink filling the periphery of the pressure generating element. An on-demand ink jet coating head displaces a pressure generating element by an applied voltage and ejects a small droplet of ink from a nozzle.

  The ink jet coating apparatus is not limited to the configuration in which the coating head and the ink storage unit are separated from each other, and a configuration in which they are integrated so as not to be separated may be used. The ink container is integrated with the application head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the apparatus for application via an ink supply member, for example, a tube. It may be in the form of supplying ink to the head.

  Further, when the ink tank is provided with a configuration for applying a preferable negative pressure to the coating head, a configuration in which an absorber is disposed in the ink storage portion of the ink tank, or a flexible ink storage bag and this On the other hand, it is possible to adopt a form having a spring portion for applying an urging force in the direction of expanding the internal volume. In addition to the serial coating method, the coating apparatus may take the form of a line printer in which coating elements are aligned over a range corresponding to the entire width of the coating medium.

  A coating film can be formed by applying the ink of the present invention onto a substrate by an ink jet coating method and then drying (removing the solvent) with a hot plate or an oven.

  The drying conditions vary depending on the type and blending ratio of the ink-containing components, but are usually 70 to 150 ° C., 5 to 15 minutes when using an oven, and 1 to 5 minutes when using a hot plate.

5.2 Curing treatment process The curing treatment is carried out, for example, on a hot plate or an oven in order to obtain the heat resistance, chemical resistance, flatness, and sufficient mechanical strength of the coating film. A pattern-like (eg, line-shaped) polyimide film is formed.

  The curing treatment is usually performed at a temperature exceeding 150 ° C. and 350 ° C. or less, preferably 200 to 300 ° C. The curing time (heating time) is, for example, 30 to 90 minutes when an oven is used, and 5 to 30 minutes when a hot plate is used. Further, the curing process is not limited to the heating process, and a UV process, an ion beam, an electron beam, a gamma ray, or the like may be used. As described above, a polyimide film is formed.

  In the case of producing a patterned polyimide film, in the present invention, ink is drawn only on a necessary portion by ink jet printing, so that the amount of material used is much less than other methods such as etching, and a photomask is used. There is no need to use it. For this reason, in the present invention, multi-product mass production is possible, and the number of steps required for production can be reduced.

  In addition, since the inkjet ink of the present invention can contain the diimide compound (A) at a high concentration as described above, a thick polyimide film can be obtained by a single jetting. For this reason, for example, when forming a thick insulating film of about 10 μm, by using the ink of the present invention, the number of times of overcoating can be reduced as compared with the conventional ink, and the manufacturing process of the insulating film can be shortened. .

6 Film substrate or silicon wafer substrate The film substrate of the present invention has a film and the above-described polyimide film formed on the film. The silicon wafer substrate of the present invention includes a silicon wafer and the polyimide film described above formed on the silicon wafer.

  A film substrate or a silicon wafer substrate can be manufactured, for example, by forming a polyimide film on a film (eg, polyimide film) on which wiring is formed or a silicon wafer according to the above-described method for manufacturing a polyimide film.

  In this invention, a well-known board | substrate can be used as a polyimide film formation object other than a polyimide film or a silicon wafer. As a substrate applicable to the present invention, for example, a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, conforming to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668, Examples include paper epoxy substrates, green epoxy substrates, and BT resin substrates.

  Other substrates applicable to the present invention include, for example, substrates made of metals such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chrome, and stainless steel (with these metals on the surface). May be a substrate); aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia), silicon oxide (silica), carbonized Silicon (silicon carbide), silicon nitride (silicon Ride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel, spodumene, and other substrates (may be substrates having such ceramics on the surface); PET (Polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylene dimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, polysulfone Resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer -A substrate made of a resin such as a liquid crystal polymer (may be a substrate having such a resin on its surface); a semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO (indium oxide) Substrates on which electrode materials such as tin) and ATO (antimony tin oxide) are formed; αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel), γGEL (gamma gel) (above, registered by Taika Corporation) (Trademark) and the like.

7 Electronic Component An electronic component of the present invention is an electronic component having the above-described film substrate and / or silicon wafer substrate. Thus, a flexible electronic component is obtained using the film substrate of the present invention. In addition, a semiconductor electronic component can be obtained using the silicon wafer substrate of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. In the following example, the ink is applied by a spin coating method or the like for convenience, but the same result can be obtained qualitatively even if the ink is applied by an ink jet method.

The names of tetracarboxylic dianhydrides, solvents, and polymerizable monomers used in Examples and Comparative Examples are abbreviated. This abbreviation is used in the following description.
Tetracarboxylic dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
Solvent EDM: Diethylene glycol methyl ethyl ether
Polymerizable monomer BAOD: 1,10-bis (acryloyloxy) decane

The measuring method of each physical property in an Example is as follows.
(I) Viscosity The viscosity of the ink jet ink obtained in Examples and Comparative Examples was measured at 25 ° C. with an E-type viscometer (VISCONIC EHD manufactured by TOKYO KEIKI).

(Ii) Warpage test A central portion 30 × 30 mm of a base material (manufactured by Toray DuPont Co., Ltd., Kapton 200H, 40 × 40 mm, thickness 50 μm) was divided into 9 blocks of 10 mm square and marked. The base material was fixed on the glass substrate (50x50 mm) using the polyimide tape with an adhesive agent so that the opposite side of the marked surface might become a surface.

  The inkjet inks obtained in Examples and Comparative Examples were applied onto a substrate by spin coating, dried on a hot plate at 80 ° C., allowed to cool for 15 minutes, and then the polyimide tape was peeled off and allowed to stand for 1 hour. Furthermore, after putting a base material into oven and heating (baking) on the conditions as described in each Example and a comparative example, it stood to cool and formed the insulating film which has the film thickness as described in each Example and a comparative example. The base material was placed on a flat surface, and the warp heights of the four corners of the base material from the flat surface were measured, and the arithmetic average value was taken as the amount of warpage.

(Iii) Bending test The ink-jet ink obtained in Examples and Comparative Examples was applied on a base material (manufactured by Toray DuPont Co., Ltd., Kapton 200H, thickness 50 μm) using an applicator. It was dried at 50 ° C. for 30 minutes using a hot plate, and further heated in an oven at 230 ° C. for 30 minutes to form an insulating film having a film thickness described in each of the examples and comparative examples on one side of the substrate. A test sample was prepared by cutting the substrate into a width of 1.5 cm and a length of 13 cm so that the TD direction (Transverse direction) of the substrate was the length direction of the test sample.
The test sample was a folding resistance tester (MITO-DA, manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a bending surface curvature radius of 0.38 mm, a bending angle of 135 °, and a tension of 4.9 N per minute. Bending was performed 30 times at a speed of 175 times, and the presence or absence of cracks at a predetermined number of times was observed.

[Synthesis of Diimide 1]
To the reaction vessel, 10.84 g (34.93 mmol) of ODPA, 9.17 g (69.86 mmol) of isoleucine and 20.10 g of EDM were added, and the mixture was heated and stirred at 170 ° C. for 3 hours. After completion of the reaction, EDM and water generated by the reaction were removed. Subsequently, 40 ml of toluene and 16.69 g (140.29 mmol) of thionyl chloride were added to the reaction vessel, and the mixture was stirred at 70 ° C. for 3 hours. The acid chloride was obtained by removing toluene and thionyl chloride.

  In another reaction vessel, 10.23 g (77.41 mmol) of diethylene glycol monovinyl ether, 8.60 g (84.99 mmol) of triethylamine and 50 ml of toluene were mixed, and the previously prepared acid chloride was added dropwise thereto.

  After completion of dropping, the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into a separating funnel and washed with 2M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. After washing, anhydrous magnesium sulfate was added to dry the solution. After drying, anhydrous magnesium sulfate was filtered off and the solvent was removed to obtain 29.66 g of diimide 1.

[Synthesis of Diimide 2]
1.63 g (5.24 mmol) of ODPA, 1.38 g (10.48 mmol) of isoleucine and 6.70 g of EDM were added to the reaction vessel, and the mixture was heated and stirred at 170 ° C. for 3 hours. After completion of the reaction, EDM and water generated by the reaction were removed. Subsequently, 30 ml of dichloromethane, 0.97 g (10.5 mmol) of ethylene glycol monovinyl ether, 0.13 g (1.06 mmol) of 4- (dimethylamino) pyridine and 3.41 g (16.53 mmol) were added to the reaction vessel. ) Dicyclohexylcarbodiimide was added and stirred at room temperature for 20 hours.

  After removing the precipitate produced by the reaction, the filtrate was poured into a separatory funnel and washed with 2M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. After washing, anhydrous magnesium sulfate was added to dry the solution. After drying, anhydrous magnesium sulfate was filtered off, and the solvent was removed to obtain 3.80 g of diimide 2.

[Synthesis of Diimide 3]
1.63 g (5.24 mmol) of ODPA, 1.38 g (10.48 mmol) of isoleucine and 6.67 g of EDM were added to the reaction vessel, and the mixture was heated and stirred at 170 ° C. for 3 hours. After completion of the reaction, EDM and water generated by the reaction were removed. Subsequently, 30 ml of dichloromethane, 1.28 g (10.5 mmol) of tetramethylene glycol monovinyl ether, 0.13 g (1.06 mmol) of 4- (dimethylamino) pyridine and 3.49 g (16. 91 mmol) of dicyclohexylcarbodiimide was added and stirred at room temperature for 20 hours.

  After removing the precipitate produced by the reaction, the filtrate was poured into a separatory funnel and washed with 2M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. After washing, anhydrous magnesium sulfate was added to dry the solution. After drying, anhydrous magnesium sulfate was filtered off and the solvent was removed to obtain 3.60 g of diimide 3.

[Synthesis of Diimide 4]
To the reaction vessel, 1.42 g (4.80 mmol) of BPDA, 1.59 g (9.61 mmol) of phenylalanine and 7.05 g of EDM were added, and the mixture was heated and stirred at 170 ° C. for 3 hours. After completion of the reaction, EDM and water generated by the reaction were removed. Subsequently, 30 ml of dichloromethane, 1.29 g (9.61 mmol) of diethylene glycol monovinyl ether, 0.13 g (1.06 mmol) of 4- (dimethylamino) pyridine and 3.39 g (16.43 mmol) were added to the reaction vessel. Of dicyclohexylcarbodiimide was added and stirred at room temperature for 20 hours.

  After removing the precipitate produced by the reaction, the filtrate was poured into a separatory funnel and washed with 2M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. After washing, anhydrous magnesium sulfate was added to dry the solution. After drying, anhydrous magnesium sulfate was filtered off and the solvent was removed to obtain 3.07 g of diimide 4.

[Example 1]
Ink jet ink 1 was obtained by mixing 4.01 g of diimide 1 and 4.01 g of EDM and stirring the mixture at room temperature for 30 minutes. The solid content concentration of the ink 1 was 50% by weight, and the viscosity was 7.8 mPa · s. When the amount of warpage of the 7 μm-thick insulating film formed from ink 1 was measured, the amount of warpage after baking at 230 ° C. for 30 minutes was an average of 0.0 mm. Subsequently, the amount of warpage after baking at 280 ° C. for 30 minutes was an average of 0.0 mm.

[Examples 2 to 5]
Inks 2 to 5 for inkjet were obtained by mixing the components shown in Table 1 in the amounts shown in Table 1 and stirring the mixture at room temperature for 30 minutes.

[Comparative Example 1]
To the reaction vessel, 3.2718 g of succinic anhydride, 7.2324 g of 3-aminopropyltriethoxysilane and 4.5024 g of tetraethoxysilane were added and refluxed at 180 ° C. for 3 hours. The reaction solution after the reaction was designated as inkjet ink 6.

  Table 1 shows the evaluation results of the viscosity and the warpage test for the inkjet inks 1 to 6. Table 2 shows the evaluation results of the bending test for the inkjet inks 1, 2 and 6.

  As is apparent from the evaluation results in Table 1, by using the ink-jet ink of the present invention, it is possible to form an insulating film with a small amount of warpage, and to have a relatively large film thickness by one ink jetting. A film can be formed. Further, as is apparent from the evaluation results of Tables 1 and 2, by adding a polymerizable monomer to the ink, in addition to the above characteristics, the insulating film can be made thicker and the flexibility can be further improved. it can.

Claims (17)

The diimide compound (A) represented by Formula (1).

[In the formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms, a plurality of Y are each independently a divalent organic group having 1 to 100 carbon atoms, and a plurality of Z are each independent. And a divalent organic group having 1 to 100 carbon atoms. ] The diimide compound according to claim 1, wherein in formula (1), a plurality of Y are each independently represented by formula (1-1), and a plurality of Z are each independently represented by formula (1-2). A).

[In the formula (1-1), m is an integer of 1 to 11; when m is 1, R ¹ is hydrogen, alkyl having 1 to 30 carbons or aryl having 6 to 10 carbons; Any hydrogen may be replaced with a hydroxyl group, a hydroxyphenyl group, a thiol group, an indole group or an imidazole group, and any —CH ₂ — in the alkyl may be replaced with —S—; When it is an integer of ˜11, R ¹ is hydrogen. ]

Wherein (1-2), R ² is a linear alkylene of 2 to 11 carbon atoms, n represents an integer of 0. ] A tetracarboxylic dianhydride (a1) represented by the formula (a1);
An amino acid (a2) represented by the formula (a2);
The diimide compound (A) according to claim 1 or 2, which is obtained by reacting the alcohol (a3) represented by the formula (a3).

[In formula (a1), X is a tetravalent organic group having 2 to 100 carbon atoms; in formula (a2), Y is a divalent organic group having 1 to 100 carbon atoms; in formula (a3) , Z is a divalent organic group having 1 to 100 carbon atoms. ] The diimide compound (A) according to claim 3, wherein the amino acid (a2) is an amino acid represented by the formula (a2-1), and the alcohol (a3) is an alcohol represented by the formula (a3-1). ).

[In the formula (a2-1), m is an integer of 1 to 11; when m is 1, R ¹ is hydrogen, alkyl having 1 to 30 carbons or aryl having 6 to 10 carbons; Any hydrogen may be replaced with a hydroxyl group, a hydroxyphenyl group, a thiol group, an indole group or an imidazole group, and any —CH ₂ — in the alkyl may be replaced with —S—; When the integer is ˜11, R ¹ is hydrogen. ]

[In Formula (a3-1), R ² is a linear alkylene having 2 to 11 carbon atoms, and n is an integer of 0 to 10. ] Tetracarboxylic dianhydride (a1) is pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylmethane tetracarboxylic dianhydride , 2, 2 [Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetra Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,3-dihydro-1,3-dioxo- 5-isobenzofurancarboxylic acid, [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] di-4,1-phenylene ester, 2,2-bis (4-hydroxyphenyl) propanedibenzoate- 3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,3-dihydro-1,3-di Xo-5-isobenzofurancarboxylic acid oxydi-4,1-phenylene ester, p-phenylenebis (trimellitic acid monoester anhydride), 4- (2,5-dioxotetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetra Carboxylic dianhydrides, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3- One or more selected from the group consisting of cyclohexene-1,2-dicarboxylic anhydride,
The amino acid (a2) is glycine, alanine, β-alanine, phenylalanine, valine, leucine, isoleucine, cysteine, methionine, serine, threonine, tyrosine, tryptophan, histidine, 4-aminobutyric acid, 6-aminohexanoic acid and 12-amino. One or more selected from the group consisting of lauric acid,
The alcohol (a3) is at least one selected from the group consisting of ethylene glycol monovinyl ether, diethylene glycol monovinyl ether and tetramethylene glycol monovinyl ether.
The diimide compound (A) according to claim 3 or 4.   An inkjet ink comprising the diimide compound (A) according to any one of claims 1 to 5 and a solvent (B).   The inkjet ink according to claim 6, wherein the content of the diimide compound (A) is 5 to 95% by weight based on the total amount of the ink.   The inkjet ink according to claim 6 or 7, wherein a viscosity at an inkjet discharge temperature is 1 to 50 mPa · s.   Furthermore, polyamic acid, imidized polymer of polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol, polyoxyethylene, polymerizable monomer, alkenyl-substituted nadiimide compound, In any one of Claims 6-8 containing 1 or more types chosen from the group which consists of a silicon amide acid compound, an epoxy resin, surfactant, an antistatic agent, a coupling agent, an epoxy hardening agent, and a polymerization initiator. The ink for inkjet described. The polyamic acid or imidized polymer thereof is obtained by using at least tetracarboxylic dianhydride and diamine, and is a polyamic acid or imidized polymer thereof having a structural unit represented by the following formula: The ink for inkjet described.

[Wherein, X is a tetravalent organic group having 2 to 100 carbon atoms, and Y is a divalent organic group having 1 to 100 carbon atoms. ]   A polyimide film obtained from the inkjet ink according to claim 6.   The polyimide film obtained by apply | coating the inkjet ink of any one of Claims 6-10 on a board | substrate by the inkjet coating method, forming a coating film, and hardening-processing the said coating film.   The manufacturing of a polyimide film including the process of apply | coating the inkjet ink of any one of Claims 6-10 on a board | substrate by the inkjet coating method, and forming the coating film, and the process of hardening the said coating film Method.   The film substrate which has a film and the polyimide film of Claim 11 or 12 formed on the said film.   An electronic component having the film substrate according to claim 14.   The silicon wafer board | substrate which has a silicon wafer and the polyimide film of Claim 11 or 12 formed on the said silicon wafer.   An electronic component comprising the silicon wafer substrate according to claim 16.