JP2013014693A - Thermosetting ink for inkjet and application of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting ink for inkjet that can form a polyimide film excellent in thermal, electrical, and mechanical characteristics, as well as can form a polyimide film of a comparatively high thickness by one jet.SOLUTION: The ink includes an acid anhydride derivative (A) that is obtained by performing reaction of a 2-10C compound being a bivalent organic group and having an acid anhydride group such as phthalic anhydride and a 4-40C or 6-60C compound being a tetravalent or hexavalent organic group and having at least two acid anhydride groups such as pyromellitic dianhydride, with trimethoxysilane and has hydrogen or a trimethylsilyl group, and a 1-100C diamine (B) that may have a carboxyl group, and satisfies 0.75<α/β<1.33, wherein αis the mole number of the acid anhydride derivative (A) and βis the mole number of the amine (B).

Description

  The present invention relates to a thermosetting ink-jet ink and its use, for example, an ink for forming an insulating film in the production of electronic components, a method for applying the ink, a polyimide film formed using the ink, and a method for producing the same, In addition, the present invention relates to an electronic component having the film substrate and the like, such as a film substrate having the polyimide film.

  Polyimide is a material widely used in the field of electronic communication because it is excellent in heat resistance and electrical insulation. In the case of using polyimide as a desired pattern film, conventionally, it has been common to form a pattern using etching or photosensitive polyimide. 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, but in order to eject and print as ink-jet inks, various parameters such as ink viscosity, solvent type and boiling point are usually optimized.

  Polyimide-based inks for inkjet use have a relatively high polyamic acid, so in order to prepare an ink having an optimum viscosity as an ink-jet ink, the content of polyamic acid in the ink is increased by increasing the proportion of the solvent. There is a need to reduce it. However, there is a problem that the film thickness of the coating film obtained by one ink jetting becomes small.

  In order to solve the above problem, for example, it has been proposed to reduce the viscosity of the ink and to increase the content of polyamic acid by controlling the weight average molecular weight of the polyamic acid to 10,000 to 50,000. For example, see Patent Document 1). However, the polymer concentration is still as small as about 15 to 20% by mass.

  On the other hand, proposals have been made to lower the viscosity and increase the concentration of the polyimide precursor solution (see, for example, Patent Documents 2 to 3). However, these documents do not discuss ink jet printing.

  Moreover, regarding the thermal crosslinking agent, a thermosetting resin composition for inkjet containing a thermal crosslinking agent and a polyimide or polybenzoxazole having a weight average molecular weight of 300 to 9,000 having a group capable of reacting with the thermal crosslinking agent. A thing is proposed (for example, refer to patent documents 4). However, since the composition requires a thermal cross-linking agent, there are problems such as storage stability and residual unreacted materials during thermosetting.

  In addition, various proposals have also been made regarding ink jet compositions in which the weight average molecular weight of the polymer is controlled (see, for example, Patent Documents 5 to 7). However, the polymers used in any of the documents are soluble polyimides having a problem in solubility because the weight average molecular weight is regulated in a very wide range.

  On the other hand, although an imide compound having a thermosetting functional group at the terminal has been disclosed (see, for example, Patent Document 8), this is also not expected to be used as an ink-jet ink, and as an ink-jet ink. No investigation has been made on the optimization of the required viscosity and solvent.

  In order to solve the above problems, a low-viscosity and high-concentration ink-jet ink has been proposed by reacting a molecular crosslinking group at the terminal of polyamic acid to control the molecular weight (see, for example, Patent Document 9). The thermal and mechanical properties were insufficient compared to conventional polyimides.

JP 2005-187596 A JP 59-164328 A JP 2000-265058 A JP 2007-314647 A JP 2000-101206 A JP 2007-297480 A JP 2006-124650 A JP-A-62-029584 JP 2009-035700 A

  An object of the present invention is to be able to form a polyimide film having good thermal, electrical, and mechanical characteristics and to form a polyimide film having a relatively thick film thickness (eg, 1 μm or more) by one jetting. The object is to provide a curable inkjet ink.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a thermosetting ink jet ink having the following constitution, and the present invention has been completed.

  The present invention has the following configuration.

［式（１）中、ｎは１以上の整数であり、ｎ＝１のとき、Ｒ¹は炭素数２〜１０の二価の有機基であり、ｎ＝２のとき、Ｒ¹は炭素数４〜４０の四価の有機基であり、ｎ＝３のとき、Ｒ¹は炭素数６〜６０の六価の有機基であり、ｎ≧４の整数のとき、Ｒ¹は炭素数２ｎ〜３０ｎの２×ｎ価の有機基であり、Ｒ²は炭素数１〜１０のアルキルまたは炭素数６〜１２の芳香族基であり、複数存在する場合は同一でも異なっていてもよく、Ｒ³は水素またはトリメチルシリルであり、複数存在する場合は同一でも異なっていてもよい。］

［式（２）中、Ｒ⁴は一般式（３）または（４）で表される基であり、Ｒ⁵は水素または炭素数１〜１００の一価の脱離可能な有機基であり、Ｒ⁵’は−ＮＨ−Ｒ⁵または−ＮＨ−ＣＯ−Ｒ⁶−ＣＯＯＨ（Ｒ⁶は炭素数２〜９８の二価の有機基である）で表される基である。］

［式（３）および（４）中、Ｒ⁷は炭素数２〜１００の二価の有機基であり、複数存在する場合は同一でも異なっていてもよく、Ｒ⁸は炭素数２〜１００の四価の有機基であり、複数存在する場合は同一でも異なっていてもよく、ｍは０〜１０００の整数である。］
［２］ （Ｂ’）一般式（５）〜（９）で表される化合物から選択される少なくとも１種をさらに含むインクである前記［１］項に記載の熱硬化性インクジェット用インク。

［式（５）中、複数あるＲ⁶はそれぞれ独立に炭素数２〜９８の二価の有機基であり、Ｒ⁷は炭素数２〜１００の二価の有機基であり、複数存在する場合は同一でも異なっていてもよく、Ｒ⁸は炭素数２〜１００の四価の有機基であり、複数存在する場合は同一でも異なっていてもよく、ｎは０〜１０００の整数である。］

［式（６）および（７）中、複数あるＲ⁶はそれぞれ独立に炭素数２〜９８の二価の有機基であり、Ｒ⁷は炭素数２〜１００の二価の有機基であり、複数存在する場合は同一でも異なっていてもよく、Ｒ⁸は炭素数２〜１００の四価の有機基であり、複数存在する場合は同一でも異なっていてもよく、ｎは１〜１０００の整数であり、ｍは０〜１０００の整数である。］

［式（８）および（９）中、Ｒ⁶は炭素数２〜９８の二価の有機基であり、Ｒ⁹は炭素数２〜１００の一価の有機基である。］
［３］ 前記式（１）中、ｎが２であり、Ｒ¹が炭素数４〜４０の四価の有機基であり、前記式（２）中、Ｒ⁵が水素である、前記［１］項または［２］項に記載の熱硬化性インクジェット用インク。
［４］ 前記式（１）中のＲ¹がテトラカルボン酸二無水物の残基であり、前記式（３）〜（４）中のＲ⁸がテトラカルボン酸二無水物の残基である、前記［３］項に記載の熱硬化性インクジェット用インク。
［５］ 溶媒（Ｃ）をさらに含む、前記［１］〜［４］の何れか一項に記載の熱硬化性インクジェット用インク。
［６］ 溶媒（Ｃ）が、乳酸エチル、エチレングリコール、プロピレングリコール、グリセリン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールメチルイソプロピルエーテル、ジエチレングリコールメチルブチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、３−メトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、シクロヘキサノン、テトラエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテルおよびγ―ブチロラクトンからなる群から選ばれる１種以上を含有する溶媒である、前記［５］項に記載の熱硬化性インクジェット用インク。
［７］ エポキシ樹脂をさらに含む、前記［１］〜［６］の何れか一項に記載の熱硬化性インクジェット用インク。
［８］ エポキシ樹脂が、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、１，３−ビス（Ｎ，Ｎ−ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−４，４’−ジアミノジフェニルメタンおよび式（Ｄ１）〜（Ｄ５）で表される化合物からなる群から選ばれる１種以上の化合物である、前記［７］項に記載の熱硬化性インクジェット用インク。

［式（Ｄ４）および（Ｄ５）中、ｎは０〜２０の整数である。］
［９］ 界面活性剤を０．００００１質量％以上、１．０質量％以下の範囲でさらに含む、前記［１］〜［８］の何れか一項に記載の熱硬化性インクジェット用インク。
［１０］ トリスアルケニル置換ナジイミド化合物およびテトラアルケニル置換ナジイミド化合物から選ばれる少なくとも１種のアルケニル置換ナジイミド化合物をさらに含む、前記［１］〜［９］の何れか一項に記載の熱硬化性インクジェット用インク。
［１１］ 顔料をさらに含む、前記［１］〜［１０］の何れか一項に記載の熱硬化性インクジェット用インク。
［１２］ 前記［１］〜［１１］の何れか一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塗布して塗膜を形成する工程、および前記塗膜を加熱処理してポリイミド膜を形成する工程を有する、インクの塗布方法。
［１３］ 基板を表面処理する工程、前記表面処理がなされた基板上に、前記［１］〜［１１］の何れか一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塗布して塗膜を形成する工程、および前記塗膜を加熱処理してポリイミド膜を形成する工程を有する、インクの塗布方法。
［１４］ 前記［１２］項または［１３］項に記載のインクの塗布方法を用いる、ポリイミド膜の製造方法。
［１５］ 前記［１４］項に記載の製造方法により形成されたポリイミド膜。
［１６］ 前記［１４］項に記載の製造方法により形成されたポリイミド膜を有する、フィルム基板、半導体ウェハまたは電子材料用基板。
［１７］ 前記［１６］項に記載のフィルム基板、半導体ウェハまたは電子材料用基板を有する電子部品。 [1] (A) A compound represented by general formula (1) (hereinafter also referred to as “compound (A)”) and (B) a compound represented by general formula (2) (hereinafter referred to as “compound (B)”). The total number of moles of the combination of —COOR ² and —COOR ³ of the compound (A) contained in the ink is α, and —NH—R ⁵ of the compound (B). A thermosetting inkjet ink, wherein α and β satisfy the formula (I): 0.75 <α / β <1.33, where β is the total number of moles.

In Expression (1), n is an integer of 1 or more, when n = 1, R ¹ is a divalent organic group having 2 to 10 carbon atoms, when n = 2, R ¹ is the number of carbon atoms 4 to 40 tetravalent organic groups, when n = 3, R ¹ is a hexavalent organic group having 6 to 60 carbon atoms, and when n ≧ 4, R ¹ is 2n to 2 carbon atoms. 30 n is a 2 × n-valent organic group, R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and may be the same or different when there are a plurality of R ³ Is hydrogen or trimethylsilyl, and when there are a plurality thereof, they may be the same or different. ]

[In the formula (2), R ⁴ is a group represented by the general formula (3) or (4), R ⁵ is hydrogen or a monovalent detachable organic group having 1 to 100 carbon atoms, R ⁵ ′ is a group represented by —NH—R ⁵ or —NH—CO—R ⁶ —COOH (R ⁶ is a divalent organic group having 2 to 98 carbon atoms). ]

[In the formulas (3) and (4), R ⁷ is a divalent organic group having 2 to 100 carbon atoms, and when a plurality of R ⁷ are present, they may be the same or different, and R ⁸ has 2 to 100 carbon atoms. It is a tetravalent organic group, and when there are a plurality thereof, they may be the same or different, and m is an integer of 0 to 1000. ]
[2] (B ′) The thermosetting inkjet ink according to item [1], which is an ink further containing at least one selected from the compounds represented by formulas (5) to (9).

[In the formula (5), a plurality of R ⁶ are each independently a divalent organic group having 2 to 98 carbon atoms, and R ⁷ is a divalent organic group having 2 to 100 carbon atoms. May be the same or different, R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and when there are a plurality thereof, they may be the same or different, and n is an integer of 0 to 1000. ]

[In the formulas (6) and (7), a plurality of R ⁶ are each independently a divalent organic group having 2 to 98 carbon atoms, and R ⁷ is a divalent organic group having 2 to 100 carbon atoms, When present in plural, they may be the same or different, R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and when present in plural, they may be the same or different, and n is an integer of 1 to 1000 And m is an integer from 0 to 1000. ]

[In formulas (8) and (9), R ⁶ is a divalent organic group having 2 to 98 carbon atoms, and R ⁹ is a monovalent organic group having 2 to 100 carbon atoms. ]
[3] In the formula (1), n is 2, R ¹ is a tetravalent organic group having 4 to 40 carbon atoms, and in the formula (2), R ⁵ is hydrogen. ] Or thermosetting inkjet ink according to item [2].
[4] R ¹ in the formula (1) is a residue of tetracarboxylic dianhydride, and R ⁸ in the formulas (3) to (4) is a residue of tetracarboxylic dianhydride. The thermosetting inkjet ink according to item [3].
[5] The thermosetting inkjet ink according to any one of [1] to [4], further including a solvent (C).
[6] The solvent (C) is ethyl lactate, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl butyl ether, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether acetate. , Ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, tetraethylene glycol dimethyl ether, triethylene glycol di- The thermosetting inkjet ink according to item [5], which is a solvent containing one or more selected from the group consisting of methyl ether and γ-butyrolactone.
[7] The thermosetting inkjet ink according to any one of [1] to [6], further including an epoxy resin.
[8] The epoxy resin is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N The thermosetting according to item [7], which is one or more compounds selected from the group consisting of '-tetraglycidyl-4,4'-diaminodiphenylmethane and compounds represented by formulas (D1) to (D5). Inkjet ink.

[In the formulas (D4) and (D5), n is an integer of 0 to 20. ]
[9] The thermosetting inkjet ink according to any one of [1] to [8], further including a surfactant in a range of 0.00001% by mass to 1.0% by mass.
[10] The thermosetting inkjet according to any one of [1] to [9], further including at least one alkenyl-substituted nadiimide compound selected from a trisalkenyl-substituted nadiimide compound and a tetraalkenyl-substituted nadiimide compound. ink.
[11] The thermosetting inkjet ink according to any one of [1] to [10], further including a pigment.
[12] A step of applying the ink-jet ink according to any one of [1] to [11] by an ink-jet coating method to form a coating film, and heat-treating the coating film to form a polyimide film A method for applying ink, comprising the step of:
[13] A step of surface-treating the substrate, on the substrate subjected to the surface treatment, the ink-jet ink according to any one of [1] to [11] is applied by an ink-jet coating method to form a coating film. An ink application method comprising a step of forming, and a step of heat-treating the coating film to form a polyimide film.
[14] A method for producing a polyimide film, which uses the ink coating method according to the item [12] or [13].
[15] A polyimide film formed by the production method according to the item [14].
[16] A film substrate, a semiconductor wafer, or an electronic material substrate having the polyimide film formed by the production method according to the item [14].
[17] An electronic component having the film substrate, semiconductor wafer or electronic material substrate according to [16].

  Hereinafter, terms in the present specification will be described.

Examples of the “monovalent organic group” include a hydrocarbon group, an alkoxy having 1 to 20 carbon atoms which may have a substituent, and an aryloxy having 6 to 20 carbon atoms which may have a substituent. , Optionally substituted amino, optionally substituted silyl, optionally substituted alkylthio (—SY ¹ ; in which Y ¹ has a substituent Optionally represents an alkyl having 2 to 20 carbon atoms.), An arylthio optionally having a substituent (—SY ² ; in the formula, Y ² may have a substituent 6 to 18 carbon atoms). . showing the aryl), which may have a substituent alkylsulfonyl (-SO ₂ Y ^3; in the formula, Y ³ represents alkyl having good 2-20 carbon atoms which may have a substituent. ), an arylsulfonyl optionally having substituent (-SO ₂ Y ^4;: in the formula, Y ⁴ is have a substituent Even if represents an aryl having 6 to 18 carbon atoms.) Can be mentioned.

  The hydrocarbon group may be saturated or unsaturated acyclic, or may be saturated or unsaturated cyclic. When the hydrocarbon is acyclic, it may be linear or branched. Examples of the hydrocarbon group include alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkynyl having 2 to 20 carbons, alkyldienyl having 4 to 20 carbons, aryl having 6 to 18 carbons, Examples thereof include alkyl aryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, cycloalkyl having 4 to 20 carbon atoms, and cycloalkenyl having 4 to 20 carbon atoms.

  The alkyl having 1 to 20 carbon atoms is preferably an alkyl having 1 to 10 carbon atoms, and more preferably an alkyl having 2 to 6 carbon atoms. Examples of the alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, and dodecanyl.

  The alkenyl having 2 to 20 carbon atoms is preferably alkenyl having 2 to 10 carbon atoms, and more preferably alkenyl having 2 to 6 carbon atoms. Examples of the alkenyl include vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, and 2-butenyl.

  The alkynyl having 2 to 20 carbon atoms is preferably alkynyl having 2 to 10 carbon atoms, and more preferably alkynyl having 2 to 6 carbon atoms. Examples of the alkynyl include ethynyl, propynyl, and butynyl.

  The alkyldienyl having 4 to 20 carbon atoms is preferably an alkyldienyl having 4 to 10 carbon atoms, and more preferably an alkyldienyl having 4 to 6 carbon atoms. Examples of the alkyldienyl include 1,3-butadienyl.

  The aryl having 6 to 18 carbon atoms is preferably an aryl having 6 to 10 carbon atoms. Examples of the aryl include phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, and phenanthryl.

  The alkylaryl having 7 to 20 carbon atoms is preferably an alkylaryl having 7 to 12 carbon atoms. Examples of the alkylaryl include o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m-cumenyl, p-cumenyl, Mesityl.

  The arylalkyl having 7 to 20 carbon atoms is preferably an arylalkyl having 7 to 12 carbon atoms. Examples of the arylalkyl include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, and 5-phenylpentyl. Is mentioned.

  The cycloalkyl having 4 to 20 carbon atoms is preferably a cycloalkyl having 4 to 10 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

  The cycloalkenyl having 4 to 20 carbon atoms is preferably a cycloalkenyl having 4 to 10 carbon atoms. Examples of the cycloalkenyl include cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

  As C1-C20 alkoxy, it is preferable that it is C1-C10 alkoxy, and it is more preferable that it is C2-C6 alkoxy. Examples of the alkoxy include ethoxy, propoxy, butoxy and pentyloxy.

  The aryloxy having 6 to 20 carbon atoms is preferably an aryloxy having 6 to 10 carbon atoms. Examples of the aryloxy include phenyloxy, naphthyloxy, and biphenyloxy.

"Alkylthio (-SY ^1;. Wherein, Y ¹ is represents an alkyl optionally 2 to 20 carbon atoms which may have a substituent)" and "alkylsulfonyl (-SO ₂ Y ^3; wherein, Y ³ is a substituted In this case, Y ¹ and Y ³ are preferably alkyl having 2 to 10 carbons, and alkyl having 2 to 6 carbons. Is more preferable. Examples of the alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, and dodecanyl.

"Arylthio (-SY ^2;. Y ² is shown an aryl having 6 to 18 carbon atoms which may have a substituent)" and "arylsulfonyl (-SO ₂ Y ^4;: in the formula, Y ⁴ is a substituent In this case, Y ² and Y ⁴ are preferably aryl having 6 to 10 carbon atoms. Examples of the aryl include phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, and phenanthryl.

  “C1-C20 hydrocarbon group”, “C1-C20 alkoxy”, “C6-C20 aryloxy”, “amino”, “silyl”, “alkylthio”, “arylthio”, “ A substituent may be introduced into “alkylsulfonyl” and “arylsulfonyl”. Examples of the substituent include ester, carboxyl, amide, alkyne, trimethylsilyl, amino, phosphonyl, thio, carbonyl, nitro, sulfo, imino, halogeno, and alkoxy. In this case, one or more substituents may be introduced at the substitutable position up to the maximum number that can be substituted, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  Examples of the “amino having a substituent” include amino, dimethylamino, methylamino, methylphenylamino, and phenylamino.

  Examples of “optionally substituted silyl” include dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxy Examples include silyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

  Heretofore, specific examples of monovalent organic groups have been exemplified. In the present specification, specific examples of the divalent organic group include groups in which the valence is further increased by one in the above-described monovalent organic group. Similarly, in the present specification, specific examples of the tetravalent and hexavalent organic groups include groups in which the valence is further increased by 3 and 5 in the monovalent organic group described above.

  In the present specification, the number of carbon atoms of the “divalent organic group having 2 to 100 carbon atoms” or “divalent organic group having 2 to 98 carbon atoms” is preferably 2 to 50, and more preferably 2 to 40. Moreover, as for carbon number of "a C2-C100 tetravalent organic group" in this specification, 2-30 are preferable.

  Examples of the crosslinkable organic group, that is, the crosslinkable group in the organic group having a crosslinkable group include alkenyl, alkynyl, cycloalkynyl, alkoxysilyl, alkenylene, alkynylene, cycloalkenylene, acrylic, and methacryl.

  Examples of “halogen” include fluorine, chlorine, bromine and iodine.

  In the following description of “Mode for Carrying Out the Invention”, the description of the above-described organic group and the like is used unless the organic group and the like are individually described.

  According to the present invention, a polyimide film having good thermal, electrical, and mechanical characteristics can be formed, and heat that can form a polyimide film having a relatively thick film thickness (eg, 1 μm or more) by one jetting. A curable inkjet ink can be provided.

  Hereinafter, the thermosetting ink-jet ink, the ink coating method, the polyimide film manufacturing method, the polyimide film, the film substrate, the semiconductor wafer and the electronic material substrate, and the electronic component according to the present invention will be described in detail including preferred embodiments. To do.

1 Thermosetting Inkjet Ink The thermosetting inkjet ink of the present invention comprises (A) a compound represented by the general formula (1) (hereinafter also referred to as “compound (A)”), and (B) a general formula. Including the compound represented by (2) (hereinafter also referred to as “compound (B)”), and the content ratio of the compound (A) and the compound (B) is in a specific range. The ink may be colored or colorless.

1.1 Compound (A)
The compound (A) is a compound represented by the general formula (1).

In formula (1), n is an integer of 1 or more.
When n = 1, R ¹ is a divalent organic group having 2 to 10 carbon atoms.
When n = 2, R ¹ is a tetravalent organic group having 4 to 40 carbon atoms, and is preferably a residue of a tetracarboxylic dianhydride described later from the viewpoint of forming a polyimide by firing.
When n = 3, R ¹ is a hexavalent organic group having 6 to 60 carbon atoms.
When n ≧ 4, R ¹ is a 2 × n-valent organic group having 2 to 30 carbon atoms, preferably a 2 × n-valent organic group having 2 to 10 carbon atoms, and forms polyimide by firing. In view of the above, it is preferably a residue of a copolymer of a radical polymerizable monomer having an acid anhydride group described later and another radical polymerizable monomer.
From the viewpoint of the heat resistance of the polyimide formed by baking, n is preferably 1 or 2, and more preferably 2.

R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and may be the same or different when a plurality of R ² are present, and R ³ is hydrogen or trimethylsilyl. It may be the same or different.

  Examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, nonyl and decanyl. Carbon number of alkyl is 1-10 normally, Preferably it is 1-4.

  Examples of the aromatic group include phenyl which may have a substituent and naphthyl which may have a substituent. Examples of the substituent include alkyl having 1 to 6 carbon atoms, carboxyl, and hydroxyl. Carbon number of an aromatic group is 6-12 normally, Preferably it is 6-10.

  The compound (A) has higher solubility in the solvent (C) than the polyamic acid and polyimide, and the concentration of the compound (A) can be increased in the ink of the present invention. Further, when the compound (A) is used, a polyimide film having high thermal and mechanical properties can be obtained as compared with the case where only the monomer type amide acid is used.

Compound (A) (wherein R ³ = hydrogen) includes, for example, compound (a1) having one or more acid anhydride groups and at least one selected from alcohol (a2) and phenols (a3) It can be obtained by reacting. The number of acid anhydride groups of the compound (a1) corresponds to the value of n of the compound (A).

Examples of commercially available compounds (A) (where R ³ = hydrogen) include product names SMA17352 and SMA2625 (manufactured by Sartomer).

  Examples of the compound (a1) include a compound (a11) having one acid anhydride group and a compound (a12) having two or more acid anhydride groups. Specific examples and preferred examples of the compound (a11) and the compound (a12) include a compound having one acid anhydride group and an acid anhydride group which will be described later in the [Description of the Invention] column of this specification. And a compound having two or more.

Compound (A) (provided that R ³ = trimethylsilyl) can be obtained, for example, by reacting compound (A) (provided that R ³ = hydrogen) with hexamethylene disilazane.

The alcohol (a2) is represented by R ² —OH (R ² has the same meaning as the alkyl having 1 to 10 carbon atoms of R ² in the formula (1)). Examples of the alcohol (a2) include methanol, ethanol, propanol, isopropanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, pentanol, heptanol, nonanol and decanol. Can be mentioned. Among these, methanol, ethanol, propanol, isopropanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, pentanol, heptanol, which are alcohols having a boiling point of 200 ° C. or less. Nonanol is preferred.

Phenols (a3) is represented by R ² -OH (R ² has the same meaning as the aromatic group having 6 to 12 carbon atoms R ² in the formula (1)). Examples of the phenols (a3) include phenol, o-cresol, m-cresol, p-cresol, salicylic acid, 1-naphthol, 2-naphthol, and catechol. Among these, phenol and o-cresol which are phenols having a boiling point of 200 ° C. or less are preferable.

<Synthesis Conditions for Compound (A)>
The compound (A) is synthesized, for example, in an excess amount of alcohol (a2) and / or an excess amount of phenols (a3) in a molar ratio with respect to the compound (a1) having one or more acid anhydride groups. The mixture can be stirred or refluxed. Here, the reaction temperature is usually 0 to 100 ° C., preferably 20 to 90 ° C., and the reaction time is usually 0.1 to 100 hours, preferably 0.2 to 20 hours, more preferably 0.00. The reaction pressure is, for example, normal pressure for 5 to 15 hours. Thereafter, the alcohol (a2) and / or the phenols (a3) added in excess can be removed under reduced pressure to obtain the compound (A).

  In the above synthesis, alcohol (a2) and / or phenols (a3) can be used as the reaction solvent, and other reaction solvents may be used as necessary.

  Examples of other reaction solvents include acetone, ethyl acetate, n-hexane, tetrahydrofuran, chloroform, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1,4 -Dioxane, anisole, methyl benzoate, ethyl benzoate, 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 monoethyl ether, propylene glycol monobutyl ether, propylene glycol Monoethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene Glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol divinyl ether, tetramethylene glycol monovinyl ether, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2- Hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone.

  Among these, when at least one selected from alcohol (a2), phenols (a3), propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether and diethylene glycol dimethyl ether is used, after the reaction Even if the reaction solvent is used as it is as an ink-jet solvent, it is preferable because an ink with little damage to the ink-jet head can be obtained.

  Only 1 type may be used for a reaction solvent, and 2 or more types may be mixed and used for it. In addition, if necessary, a solvent other than the reaction solvent can be mixed with the reaction solvent.

  When alcohol (a2) and / or phenols (a3) are used as the reaction solvent, the reaction is carried out with respect to 100 parts by mass of the compound (a1) having one or more acid anhydride groups from the viewpoint of promoting the reaction efficiently. The solvent is preferably used in an amount of 200 parts by mass or more, and more preferably 1000 parts by mass or more. The upper limit of the amount of the reaction solvent used is not particularly limited, and is, for example, about 10000 parts by mass with respect to 100 parts by mass of the compound (a1) having one or more acid anhydride groups.

  The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a method in which the compound (a1) and the alcohol (a2) and / or phenols (a3) are mixed at the same time, a method in which the above components are added to other reaction solvents at the same time, an alcohol (a2) and / or a phenols (a3 ) Is dissolved in the other reaction solvent and then the compound (a1) is added, the compound (a1) is dissolved in the other reaction solvent, and the alcohol (a2) and / or phenols (a3) is added. Any method can be used, such as

<Contents of Compound (A) and Compound (B)>
The total number of moles of the combination of —COOR ² and —COOR ³ of compound (A) contained in the thermosetting inkjet ink of the present invention is α, and the total number of moles of —NH—R ⁵ of compound (B) is Let β. In the thermosetting inkjet ink of the present invention, the compound (A) and the compound (B) are included so as to satisfy the following conditions. That is, α / β is more than 0.75 and less than 1.33, preferably 0.9 or more and 1.11 or less. Here, in the compound (A), the total number of moles of said set is a -COOR ² and -COOR ³ as one set, counting the set as one. In the compound (B), the total number of moles is counted as two when two —NH—R ⁵ is contained in one molecule.
When α / β is in the above range, it is preferable from the viewpoint that the amount of unreacted compound (A) and compound (B) at the time of firing is small and the properties of the film after firing are good. Each of the above groups can react with each other to form an imide group.

1.2 Compound (B)
The compound (B) is a compound represented by the general formula (2). In the present invention, a strong polyimide film is formed by a dehydration reaction between the compound (B) and the compound (A).

In the formula (2), R ⁴ is a group represented by the general formula (3) or (4). When the group represented by the general formula (3) is used in the general formula (2), an amide solvent In addition, a lactone solvent or a glycol solvent that causes little damage to the ink jet head can be used, which is preferable. R ⁵ ′ is a group represented by —NH—R ⁵ or —NH—CO—R ⁶ —COOH. R ⁵ is hydrogen or a monovalent detachable organic group having 1 to 100 carbon atoms (hereinafter also referred to as “leaving group”). If there is a leaving group, a reaction for elimination is required. From such a viewpoint, hydrogen is preferable. R ⁶ is a divalent organic group having 2 to 98 carbon atoms, and is preferably an organic group having crosslinkability.

As the compound (B), a total of compounds in which R ⁶ is an organic group having a crosslinking group is preferably used in an amount of 50 mol% or more, more preferably 75 mol% or more, based on the entire compound (B ′). .

  Examples of the leaving group include a t-butoxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an allyloxycarbonyl group. The leaving group acts as a protecting group at the molecular end of the compound (B). The number of carbon atoms in the leaving group is preferably 2-50, more preferably 2-15.

In formulas (3) and (4), R ⁷ is a divalent organic group having 2 to 100 carbon atoms, and when a plurality of R ⁷ are present, they may be the same or different. R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and is preferably a residue of a tetracarboxylic dianhydride described later from the viewpoint of forming a polyimide by firing, and the same when there are a plurality of R ⁸ But it can be different. m is an integer of 0 to 1000, preferably an integer of 0 to 800, and more preferably an integer of 0 to 650.

In the compound (B), when R ⁵ is a leaving group, the organic group is removed, the compound (B) becomes a primary amine, dehydrates with the compound (A) to form a polyamic acid, and thus a strong polyimide. A membrane is obtained.

  Examples of the compound (B) include diamine (b1), a compound obtained by protecting amino of diamine (b1) with a leaving group, diamine (b1) and compound (b3) having one acid anhydride group. Reaction product (amidic acid), reaction product of diamine (b1) and compound (b2) having two or more acid anhydride groups (polyamic acid or imidized product thereof), diamine (b1) and two acid anhydride groups Examples include a reaction product (polyamic acid or imidized product thereof) of the compound (b2) having the above and a compound (b3) having one acid anhydride group, and a compound obtained by protecting amino of the reaction product with a leaving group. .

  Specific examples and preferred examples of the diamine (b1), the compound (b2) having two or more acid anhydride groups, and the compound (b3) having one acid anhydride group are as follows. The compound which has 2 or more of the diamine and acid anhydride group which are mentioned later in the form of this form.

<Weight average molecular weight of compound (B)>
Of the compound (B), the polyamic acid and its imide compound have a weight average molecular weight (Mw) of usually 900 to 7,500, preferably 900 to 3,500, and more preferably 900 to 2,500. The compound (B) whose Mw is not less than the lower limit value is chemically and mechanically stable without being evaporated in the step of forming a polyimide film by heat treatment. The compound (B) having an Mw of not more than the above upper limit has good solubility in the solvent (C) and can reduce the viscosity of the ink, so that the thickness of the resulting polyimide film can be increased. is there. The measurement conditions for Mw are as described in the examples.

<Synthesis conditions of compound (B)>
An example of the synthesis conditions for the compound (B) will be described. Compound (B) can be obtained, for example, by a method of reacting diamine (b1) with compound (b2) having two or more acid anhydride groups. Moreover, you may make the compound (b3) which has one or more acid anhydride groups react as needed. If necessary, the amino at the molecular end may be protected with a leaving group.

  The reaction temperature is usually 0 to 100 ° C., preferably 4 to 80 ° C., the reaction time is usually 0.2 to 20 hours, preferably 0.5 to 10 hours, and the reaction pressure is, for example, normal pressure.

The compound in which R ⁴ is represented by the general formula (4) in the compound (B) is obtained, for example, by imidizing the compound in which R ⁴ is represented by the general formula (3) in the compound (B). Can do.

The imidization can proceed by a thermal method or a chemical method using a dehydration catalyst and a dehydrating agent. Preferably, imidization is advanced by a thermal method that can be used as a component of the ink without performing a purification treatment. More preferably, R ⁴ in the compound (B) is synthesized in a reaction solvent and then imidized by refluxing. The reflux conditions vary depending on the reaction solvent used, but are preferably 140 to 230 ° C. for 1.5 to 10 hours. When the reflux temperature is 140 ° C. or higher, imidization sufficiently proceeds and a strong film can be obtained. When the reflux temperature is 230 ° C. or lower, the solvent can be refluxed even if a solvent having a relatively high boiling point is used.

  The diamine (b1), the compound (b2) having two or more acid anhydride groups, and the compound (b3) having one acid anhydride group that can be used when synthesizing the compound (B) are each only one kind. May be used, or two or more kinds may be mixed and used.

  Examples of the reaction solvent that can be used when synthesizing the compound (B) include the above-mentioned other reaction solvents that can be used for the synthesis of the compound (A), and preferred reaction solvents are also the same.

  Only 1 type may be used for a reaction solvent, and 2 or more types may be mixed and used for it. In addition, if necessary, a solvent other than the reaction solvent can be mixed with the reaction solvent.

  From the viewpoint of efficiently proceeding with the reaction, the reaction solvent is a total of reaction raw materials such as diamine (b1), a compound (b2) having two or more acid anhydride groups, and a compound (b3) having one acid anhydride group. It is preferable to use 100 parts by mass or more with respect to 100 parts by mass, and preferably 500 parts by mass or more. The upper limit of the usage amount of the reaction solvent is not particularly limited, and is, for example, about 1000 parts by mass with respect to 100 parts by mass of the reaction raw materials.

  There is no particular limitation on the order of adding the reaction raw materials to the reaction system. That is, a method in which a diamine (b1) and a compound (b2) having two or more acid anhydride groups are simultaneously added to a reaction solvent, and two acid anhydride groups are dissolved after the diamine (b1) is dissolved in the reaction solvent. Any method such as a method of adding the compound (b2) having the above can be used. In the case of a combination of other reaction raw materials, a method according to the above method can be used.

  In addition, compound (B) may be synthesized in the presence of compound (A). That is, a method in which the diamine (b1), the compound (b2) having two or more acid anhydride groups, and the compound (A) are simultaneously added to the reaction solvent, and after the diamine (b1) is dissolved in the reaction solvent A method of adding the compound (b2) having two or more acid anhydride groups and the compound (A), and reacting the diamine (b1) with the compound (b2) having two or more acid anhydride groups in advance to form a polyamic acid Any method such as a method of adding the compound (A) after synthesizing can be used. In the case of a combination of other reaction raw materials, a method according to the above method can be used.

<Content of Compound (B)>
In the thermosetting ink jet ink of the present invention, the content of the compound (B) (the total content of the compound (B) and the compound (B ′) when the compound (B ′) described later) is used is the total amount of the ink. 10-60 mass% is preferable with respect to mass, 14-55 mass% is more preferable, and 18-50 mass% is further more preferable. When the concentration of the compound (B) and the compound (B ′) used as necessary is within the above range, the film thickness of the coating film obtained by one ink jetting is optimal, and the jetting accuracy is high. preferable. In the ink of the present invention, low viscosity suitable for ink jet printing, and high concentration of ink (solid content concentration of 20% by mass or more) by compound (B) and compound (B ′) used as necessary Both are possible.

1.3 Compound (B ′)
The thermosetting ink jet ink of the present invention has at least one selected from the compounds represented by the general formulas (5) to (9) in addition to the above-mentioned compounds (A) and (B) (hereinafter “compound ( B ′) ”))) may also be included. Among these, the compound represented by the general formula (5) is preferable because not only an amide solvent but also a lactone solvent or a glycol solvent that causes little damage to the ink jet head can be used.

By using the compound (B ′), a dehydration reaction between the compound (A) and the compound (B ′), and when R ⁶ is an organic group having a crosslinking group, the compound (B) and the compound (B ′) A strong polyimide film is formed by the crosslinking reaction and the crosslinking reaction between the compounds (B ′).

In formula (5), a plurality of R ⁶ are each independently a divalent organic group having 2 to 98 carbon atoms, and preferably an organic group having crosslinkability. R ⁷ is a divalent organic group having 2 to 100 carbon atoms, and when a plurality of R ⁷ are present, they may be the same or different. R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and is preferably a residue of a tetracarboxylic dianhydride described later from the viewpoint of forming a polyimide by firing, and the same when there are a plurality of R ⁸ But it can be different. n is an integer of 0 to 1000, preferably an integer of 1 to 800, and more preferably an integer of 1 to 650.

  Examples of the compound represented by the general formula (5) include a reaction product of a diamine (b1) and a compound (b3) having one acid anhydride group (amidic acid, n = 0), a diamine (b1), and And a reaction product (polyamic acid, n ≧ 1) of the compound (b2) having two or more acid anhydride groups and the compound (b3) having one acid anhydride group.

In formulas (6) and (7), a plurality of R ⁶ are each independently a divalent organic group having 2 to 98 carbon atoms, and preferably an organic group having crosslinkability. R ⁷ is a divalent organic group having 2 to 100 carbon atoms, and when a plurality of R ⁷ are present, they may be the same or different. R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and is preferably a residue of a tetracarboxylic dianhydride described later from the viewpoint of forming a polyimide by firing, and the same when there are a plurality of R ⁸ But it can be different. n is an integer of 1-1000, preferably an integer of 1-800, more preferably an integer of 1-650. m is an integer of 0 to 1000, preferably an integer of 0 to 800, and more preferably an integer of 0 to 650.

  Examples of the compound represented by the general formula (6) include a compound obtained by imidizing a reaction product (polyamide acid) of a diamine (b1) and a compound (b2) having two or more acid anhydride groups, and an acid. And a reaction product (amide acid) with compound (b3) having one anhydride group.

  Examples of the compound represented by the general formula (7) include compounds obtained by imidizing a reaction product (amidic acid) of the diamine (b1) and the compound (b3) having one acid anhydride group (m = 0), a compound obtained by imidizing a reaction product (polyamic acid) of a diamine (b1), a compound (b2) having two or more acid anhydride groups and a compound (b3) having one acid anhydride group ( m ≧ 1). Examples of the former include bisalkenyl-substituted nadiimide (when m = 0 and compound (b3) is an alkenyl-substituted nadic acid anhydride), bismaleimide (when m = 0 and compound (b3) is maleic anhydride). Can be mentioned. Alkenyl-substituted nadiimide is preferable as the compound (B ′) because it has good solubility in the solvent (C).

In formulas (8) and (9), R ⁶ is a divalent organic group having 2 to 98 carbon atoms, and R ⁹ is a monovalent organic group having 2 to 100 carbon atoms. R ⁶ and R ⁹ are preferably each independently an organic group having crosslinkability.

  Examples of the compound represented by the general formula (8) include a reaction product (amide acid) of a compound (b3) having one acid anhydride group and a monoamine (b4). Examples of the compound represented by the general formula (9) include a compound obtained by imidizing a reaction product (amidic acid) of a compound (b3) having one acid anhydride group and a monoamine (b4). . Examples of the latter include monoalkenyl-substituted nadiimide (when compound (b3) is alkenyl-substituted nadic acid anhydride) and monomaleimide (when compound (b3) is maleic anhydride). Alkenyl-substituted nadiimide is preferable as the compound (B ′) because it has good solubility in the solvent (C).

As the compound (B ′), it is preferable that R ⁶ and / or R ⁹ is an organic group having a crosslinking group in total, and is used in an amount of 50 mol% or more based on the entire compound (B ′), and 75 mol% It is more preferable to use the above.

  Specific examples and preferred examples of the diamine (b1), the compound (b2) having two or more acid anhydride groups, the compound (b3) having one acid anhydride group and the monoamine (b4) include [ Examples of diamines, compounds having two or more acid anhydride groups, compounds having one acid anhydride group, and monoamines, which will be described later in the “Mode for Carrying Out the Invention” column.

  Specific examples and preferred examples of the monoalkenyl-substituted nadiimide and bisalkenyl-substituted nadiimide include the compounds described later in the “Description of Embodiments” column of this specification.

<Weight Average Molecular Weight of Compound (B ′)>
Of the compound (B ′), the polyamic acid and its imide compound have a weight average molecular weight (Mw) of usually 900 to 7,500, preferably 900 to 3,500, more preferably 900 to 2,500. The compound (B ′) having Mw equal to or higher than the lower limit value is chemically and mechanically stable without being evaporated in the step of forming a polyimide film by heat treatment. The compound (B ′) having an Mw of not more than the above upper limit has good solubility in the solvent (C) and can reduce the viscosity of the ink, so that the thickness of the resulting polyimide film can be increased. It is. The measurement conditions for Mw are as described in the examples.

<Synthesis Conditions for Compound (B ′)>
The reaction conditions (reaction temperature, imidization method) for synthesizing the compound (B ′) can be performed in the same manner as the reaction conditions for synthesizing the compound (B).

  Diamine (b1) that can be used in the synthesis of compound (B ′), compound (b2) having two or more acid anhydride groups, compound (b3) having one acid anhydride group, monoamine (b4) May be used alone or in combination of two or more.

  Examples of the reaction solvent that can be used when synthesizing the compound (B ′) include the above-mentioned other reaction solvents that can be used for the synthesis of the compound (A), and preferred reaction solvents are also the same.

  Only 1 type may be used for a reaction solvent, and 2 or more types may be mixed and used for it. In addition, if necessary, a solvent other than the reaction solvent can be mixed with the reaction solvent.

  From the viewpoint of promoting the reaction efficiently, the reaction solvent is diamine (b1), compound (b2) having two or more acid anhydride groups, compound (b3) having one acid anhydride group, monoamine (b4), and the like. It is preferable to use 100 parts by mass or more, preferably 500 parts by mass or more, based on a total of 100 parts by mass of the reaction raw materials. The upper limit of the usage amount of the reaction solvent is not particularly limited, and is, for example, about 1000 parts by mass with respect to 100 parts by mass of the reaction raw materials.

<Content of Compound (B ′)>
In the thermosetting inkjet ink of the present invention, the content of the compound (B ′) is preferably 10 to 60% by mass, and 14 to 55% by mass, based on the total mass of the ink, together with the compound (B) described above. Is more preferable, and 18-50 mass% is further more preferable. When the concentration of the compound (B ′) is in the above range, the film thickness of the coating film obtained by one ink jetting is optimal, which is preferable in terms of high jetting accuracy. In the ink of the present invention, it is possible to achieve both low viscosity suitable for inkjet printing and high concentration of ink (solid content concentration of 20% by mass or more).

1.4 Solvent (C)
The inkjet ink of the present invention can be obtained, for example, by dissolving the compound (A) and the compound (B) in the solvent (C). Therefore, the solvent (C) is not particularly limited as long as it can dissolve the components (A) and (B). Moreover, even if it is a solvent that does not dissolve the components (A) and (B) by itself, it becomes a mixed solvent that can dissolve the components (A) and (B) by mixing with other solvents. If present, the solvent can also be used as the solvent (C).

  The boiling point of the solvent (C) is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. If the boiling point is too low, the solvent in the ink near the printer head nozzles will evaporate. As a result, the viscosity of the ink changes and the ink cannot be ejected, or the ink components may solidify and precipitate. If the boiling point is too high, the drying of the ink after printing is too slow, and the printing pattern may deteriorate.

  Examples of the solvent (C) include ethyl lactate, ethylene glycol, propylene glycol, glycerin, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, 1,4-dioxane, γ- Butyrolactone, anisole, methyl benzoate, ethyl benzoate, 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 monoethyl ether, propylene glycol monobutyl ether, propylene glycol Monomethyl ether acetate, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol Propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene group Recall monomethyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetramethylene glycol monovinyl ether, 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-i Dazorijinon, N- methyl -ε- caprolactam include carbamates.

  Among these solvents, for example, from the viewpoint of improving the durability of an inkjet head, ethyl lactate, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl butyl ether, diethylene glycol Dibutyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, tetraethylene Recall dimethyl ether, at least one selected from triethylene glycol dimethyl ether and γ- butyrolactone are preferred.

  Among the solvents exemplified above, when the durability of the inkjet head and the accuracy of jetting are problematic, it is preferable to reduce the use of an amide solvent. In such a case, the content of the amide solvent is preferably 0 to 30% by mass and more preferably 0 to 20% by mass with respect to the total amount of the solvent (C).

  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-methylcaprolactam And carbamate esters.

Only 1 type may be used for a solvent (C), and 2 or more types may be mixed and used for it.
The solvent (C) is preferably used in a range where the solid content concentration in the inkjet ink is 20 to 80% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 30% by mass.

1.5 Additive The ink-jet ink of the present invention may contain an additive depending on the intended properties. Examples of the additive include, for example, tris and tetraalkenyl substituted nadiimides that are not included in the compound (B ′) among epoxy resins and alkenyl substituted nadiimides, acrylic resins, polymerizable monomers, surfactants, compounds (B) and (B ′ ) Other than polyamic acid, polyimide, polyamide, polyester, pigment, antistatic agent, coupling agent, curing agent (eg epoxy curing agent, alkenyl-substituted nadiimide curing agent), dye, pH adjuster, rust inhibitor, antiseptic Agents, antifungal agents, antioxidants, anti-reduction agents, evaporation accelerators, chelating agents, and water-soluble polymers.

1.5.1 Epoxy Resin In the present invention, a compound having at least one oxirane ring or oxetane ring is referred to as an epoxy resin. In the present invention, as the epoxy resin, a compound having two or more oxirane rings is preferably used.

  Examples of the epoxy resin include phenol novolak type, cresol novolak type, bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, bisphenol S type, trisphenol methane type, tetraphenol ethane type, Xylenol type, biphenol type, glycidyl ester type epoxy resin; alicyclic or heterocyclic epoxy resin; epoxy resin having adamantane skeleton; epoxy resin having dicyclopentadiene type or naphthalene type structure; N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane , Formulas (D1) to (D5 A compound represented by the polymerization of a monomer having an oxirane ring, a copolymer of a monomer with other monomers having an oxirane ring.

  In formulas (D4) and (D5), n is an integer of 0-20.

  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, and 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 Coalescence is mentioned. It is preferable that the ink-jet ink contains these epoxy resins because the heat resistance of the coating film formed from the ink-jet ink is improved.

Various commercially available products can be used as the epoxy resin.
Examples of commercially available epoxy resins include:
TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals), epoxy resin 828, 834, 1001, 1004, and 1010 (trade name; manufactured by Mitsubishi Chemical), Epicron 840, 850, 1050, and 1050 (product) Name: manufactured by DIC), Epototo YD-011, YD-013, YD-127, YD-128 (trade name; manufactured by Toto Kasei), D.E.R.317, 331, 661, 664 (trade name; manufactured by Dow Chemical Company), Araldite 6071, 6084, GY250, GY260 (trade name; manufactured by BASF), Sumi-Epoxy ESA-011, ESA-014, ELA-115, Bispheno such as ELA-128 (trade name; manufactured by Sumitomo Chemical Co., Ltd.), A.E.R. 330, 331, 661, and 664 (trade name; manufactured by Asahi Kasei Co., Ltd.) A type epoxy resin;

  Epoxy resin 152, 154 (trade name; manufactured by Mitsubishi Chemical Corporation), D.E.R.431, 438 (trade name; manufactured by Dow Chemical Company), Epicron N-730, N-770, N-865 (Trade name; manufactured by DIC), Epototo YDCN-701, YDCN-704 (trade name; manufactured by Toto Kasei), Araldite ECN1235, ECN1273, ECN1299 (trade name; manufactured by BASF), XPY307, EPPN-201 , EOCN-1025, EOCN-1020, EOCN-104S, RE-306 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Sumi-epoxy ESCN-195X, and ESCN-220 (trade name; manufactured by Sumitomo Chemical Co., Ltd.), A. Novolac epoxy resins such as ER ECN-235 and ECN-299 (trade name; manufactured by ADEKA);

  Epicron 830 (trade name; manufactured by DIC), epoxy resin 807 (trade name; manufactured by Mitsubishi Chemical Corporation), Epototo YDF-170 (trade name; manufactured by Tohto Kasei Co., Ltd.), YDF-175, YDF-2001, YDF-2004, Bisphenol F type epoxy resin such as Araldite XPY306 (trade name; manufactured by BASF); Hydrogenated bisphenol A type epoxy resin such as Epototo ST-2004, ST-2007, ST-3000 (trade name; manufactured by Toto Kasei Co., Ltd.) ;

  Cycloside 2021 (trade name; manufactured by Daicel Chemical Industries Ltd.), Araldite CY175, CY179, CY184 (trade name; manufactured by BASF Corp.), and the like; YL-933 (trade name; manufactured by Mitsubishi Chemical Corporation), Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 (trade names; manufactured by Dow Chemical Company); Bixylenols such as YL-6056, YX-4000, and YL-6121 (trade names; manufactured by Mitsubishi Chemical Corporation) Molds or biphenol type epoxy resins or mixtures thereof;

  Bisphenol S type epoxy resin such as EBPS-200 (trade name; manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (trade name; manufactured by ADEKA), EXA-1514 (trade name; manufactured by DIC); 157S (trade name; Bisphenol A novolak type epoxy resin such as Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as YL-931 (trade name; manufactured by Mitsubishi Chemical Corporation), Araldite 163 (trade name; manufactured by BASF);

  An epoxy resin having an adamantane skeleton, such as ADAMANTATE-X-E-201, ADAMANTATE-X-E-202, ADAMANTATE-X-E-203, ADAMANTATE-X-E-204 (trade name; manufactured by Idemitsu Kosan);

  Heterocyclic epoxy resins such as Araldite PT810 (trade name; manufactured by BASF) and TEPIC (trade name; manufactured by Nissan Chemical Industries); HP-4032, EXA-4750, EXA-4700 (trade name; manufactured by DIC), etc. And an epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H, and HP-7200HH (trade name; manufactured by DIC).

  Among these epoxy resins, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type Epoxy resin, trisphenolmethane type epoxy resin, tetraphenolethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Preferred are cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and epoxy resins represented by formulas (D1) to (D5);

  N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4, 4′-diaminodiphenylmethane and epoxy resins represented by the formulas (D1) to (D5) are particularly preferable in that a cured film having excellent chemical resistance can be obtained.

  As the epoxy resin, only one kind may be used, or two or more kinds may be mixed and used.

  When using an epoxy resin, the content of the epoxy resin is preferably 0.01 to 20% by mass, and more preferably 1 to 10% by mass with respect to the total mass of the inkjet ink. When the content of the epoxy resin is in the above range, the heat resistance, chemical resistance and flatness of the coating film formed from the ink jet ink are good.

1.5.2 An alkenyl-substituted nadiimide other than the compound (B ′) other than the compound (B ′) is a compound having at least three alkenyl-substituted nadiimide structures in the molecule. The alkenyl substituted nadiimide compound represented by this is mentioned.

In formula (F-1), R ¹⁰ and R ¹¹ 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, and l is an integer of 3 or 4.

In the formula (F-1), when l = 3, R ¹² is a group represented by the general formula (F-2) or (F-3).

In formula (F-2), R represents hydrogen, fluorine, chlorine, —OH, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₂ CF ₂ H, —OCF. ₂ CFHCF ₃ or alkyl having 1 to 10 carbon atoms. In formula (F-2) and formula (F-3), R ¹³ , R ¹⁴ and R ¹⁵ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl. 1,4-phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is —O— or —CH═. It may be replaced with CH-, and any hydrogen may be replaced with fluorine.

When l = 3 in Formula (F-1), R ¹² is a group represented by Formula (F-2-1), Formula (F-3-1), or Formula (F-3-2). It is preferable.

In formula (F-2-1), R represents hydrogen, —OH, or alkyl having 1 to 10 carbons. In formula (F-3-2), R ¹³ , R ¹⁴ and R ¹⁵ are each independently 1,2-ethylene or 1,4-butylene.

In the formula (F-1), when l = 4, R ¹² is a group represented by the general formula (F-4).

In the formula (F-4), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a single bond, trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4 -Phenylene, 1,4-phenylene in which hydrogen may be replaced by fluorine, or alkylene having 1 to 10 carbon atoms, and any methylene that is not adjacent to each other in alkylene is replaced by -O- or -CH = CH- Any hydrogen may be replaced by fluorine.

In the formula (F-1), when l = 4, R ¹² is preferably a group represented by the general formula (F-4-1).

In formula (F-1), R ¹⁰ and R ¹¹ are preferably each independently hydrogen or alkyl having 1 to 6 carbons. R ¹² is a group represented by the formula (F-2-1) when l = 3 (wherein R is hydrogen or —OH), a group represented by the formula (F-3-1), A group represented by the formula (F-3-2) (wherein R ^{13 to} R ¹⁵ are 1,2-ethylene) is preferred; when l = 4, the formula (F-4-1) It is preferable that it is group represented by these. The ink of the present invention may contain at least two of these alkenyl-substituted nadiimides.

<Synthesis of tris and tetraalkenyl substituted nadiimide>
The alkenyl-substituted nadiimide is, for example, an alkenyl-substituted nadiimide compound obtained by reacting a triamine or tetraamine with an alkenyl-substituted nadic acid anhydride represented by the general formula (F-1 ′).

R ¹⁰ and R ¹¹ in formula (F-1 ') has the same meaning as R ¹⁰ and R ^11, respectively formula (F-1).

The alkenyl-substituted nadiimide compound can be synthesized, for example, as follows.
(1) In the case of a trisalkenyl-substituted nadiimide compound in which l is 3, tetrakisalkenyl in which l is 4 is mixed with 3.0 to 5.0 mol of alkenyl-substituted nadic acid anhydride with respect to 1.0 mol of triamine. In the case of a substituted nadiimide compound, 4.0 to 6.0 moles of alkenyl-substituted nadic acid anhydride is mixed with 1.0 mole of tetraamine, and (2) subsequently, for example, an arbitrary solvent or two or more kinds at room temperature. It is made to melt | dissolve in the mixed solvent to make a solution, and it is made to react by stirring and holding for 0.5 to 30 hours.

  Examples of the solvent include benzene, toluene, xylene, mesitylene, methylnaphthalene, tetralin, chloroform, trichlene, tetrachloroethylene, chlorobenzene, dioxane, tetrahydrofuran, hexamethylene ether, anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, N, Examples thereof include N-dimethylformamide and dimethyl sulfoxide.

  The solvent is removed by drying at 20-80 ° C. under reduced pressure to obtain amic acid. The amic acid is refluxed in the above solvent for 0.5 to 30 hours, near the boiling point of the solvent, or the compound itself is heated at 160 to 200 ° C. for dehydration and ring closure, and then the solvent is dried under reduced pressure. The target compound can be obtained. The target compound can be confirmed by NMR and IR.

<Tris alkenyl substituted nadiimide>
Examples of the trisalkenyl-substituted nadiimide compound in which l is 3 include tris {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) ethyl} amine, tris {4 -(Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, tris {4- (allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximido) phenyl} hydroxymethane.

<Tetrakis alkenyl substituted nadiimide>
Examples of the tetrakisalkenyl-substituted nadiimide compound in which l is 4 include tetrakis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane.

  Alkenyl-substituted nadiimide is a low molecular weight imide monomer with a bulky structure, so it is soluble in most organic solvents and stable even without storage or crystallization even when stored in solution for a long period of time. Can be used. The alkenyl-substituted nadiimide forms a polyimide having a three-dimensional crosslinked structure by heating. The polyimide exhibits good heat resistance, mechanical properties, electrical properties, and chemical resistance.

1.5.3 Acrylic resin The acrylic resin is not particularly limited as long as it is a homopolymer or a copolymer of monomers having an acrylic group and / or a methacrylic group. Examples of the acrylic resin include a monofunctional polymerizable monomer having hydroxyl, a monofunctional polymerizable monomer having no hydroxyl, a bifunctional (meth) acrylate, or a trifunctional or higher polyfunctional (meth) acrylate homopolymer, or these And a copolymer of these monomers. Only one type of acrylic resin may be used, or two or more types may be mixed and used.

  Specific examples of the monofunctional polymerizable monomer having hydroxyl include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono ( And (meth) acrylate. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferable from the viewpoint that the formed film can be made flexible.

Specific examples of the monofunctional polymerizable monomer having no hydroxyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3-methyl-3- (meth) acryloxy. Methyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3 -(Meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (meth) acrylic acid, methyl (meth ) Acrylate, ethyl (meth) acrylate, isopropyl (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meta ) Acrylate, (meth) acrylamide, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, glycerol Mono (meth) acrylate, polymethyl methacrylate macromonomer, N-acryloylmorpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, ethylene oxide adduct of lauryl alcohol (Meth) acrylate, (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 [2- (meth) acryloyloxyethyl], cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl] Is mentioned.

  Specific 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, pentaerythritol. Diacrylate monostearate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-bis (acryloyloxy) decane, 1,4-cyclohexanedi Methanol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, trimethylolpropane diacrylate Acrylate, dipentaerythritol diacrylate.

  Specific examples of trifunctional or higher polyfunctional (meth) acrylates are trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified Trimethylolpropane 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, Pentaerythritol 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.

  As the acrylic resin, other monomers may be copolymerized. For example, p-vinylphenyl-3-ethyloxe-3-ylmethyl ether, styrene, methylstyrene, chloromethylstyrene, N-cyclohexylmaleimide, N- Examples include phenylmaleimide, vinyltoluene, and polystyrene macromonomer.

  Although the acrylic resin density | concentration in the ink for thermosetting inkjets of this invention is not specifically limited, 0.1-20 mass% is preferable and 1-10 mass% is more preferable. Within such a concentration range, the cured film formed from the thermosetting inkjet ink of the present invention has good heat resistance, chemical resistance, and flatness.

1.5.4 Polymerizable monomer 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 polyfunctional (metafunctional) having three or more functions. ) Acrylate and other monomers, and specific examples thereof are as described in the description of the acrylic resin.

  As the polymerizable monomer, only one kind may be used, or two or more kinds may be mixed and used.

  When the polymerizable monomer is used, the content of the polymerizable monomer in the inkjet ink is preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass with respect to the total mass of the inkjet ink. When the content of the polymerizable monomer is within the above range, the heat resistance, chemical resistance, and flatness of the coating film formed from the inkjet ink are good.

1.5.5 Polymer Compound The thermosetting ink-jet ink of the present invention is selected from polyamic acid, polyimide, polyamide and polyester other than compounds (B) and (B ′) for imparting flexibility and heat resistance. It may contain at least one kind of polymer compound. In particular, a polymer compound having a weight average molecular weight of 1,000 to 10,000 is excellent in solubility in the solvent (C) and is preferable as a component contained in the thermosetting inkjet ink of the present invention. From the viewpoint of solubility in the solvent (C), the weight average molecular weight of the polymer compound is more preferably 1,000 to 7,500, still more preferably 1,000 to 5,000, and particularly preferably. 1,000 to 2,000.

  When the weight average molecular weight is 1,000 or more, it is chemically and mechanically stable without being evaporated by heat treatment. Moreover, since the solubility with respect to the solvent of a high molecular compound is especially high as a weight average molecular weight is 2,000 or less, since the density | concentration of the high molecular compound in the thermosetting inkjet ink of this invention can be made high, The flexibility and heat resistance of the coating film obtained by applying the ink can be improved.

  The weight average molecular weight 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 mass, and gel is prepared using Tosoh Co., Ltd. columns G4000HXL, G3000HXL, G2500HXL and G2000HXL with THF as a developing agent. It can be determined by measuring by a permeation chromatography (GPC) method and converting to polystyrene.

  The concentration of the polymer compound in the thermosetting ink jet ink of the present invention is usually 0 to 20% by mass, preferably 0 to 10% by mass. Such a concentration range is preferable because good characteristics can be imparted as an insulating film.

1.5.6 Surfactants Surfactants include fluorine surfactants, acrylic surfactants, and silicone surfactants because they can adjust the surface tension of ink and improve coating properties. There is no particular limitation as long as it has a surfactant effect and reduces the surface tension of the ink.

  When an ink containing an acrylic surfactant is used, there is a tendency that a film having excellent patternability can be obtained. When an ink containing a silicone surfactant is used, there is a tendency that a film having excellent patternability can be obtained.

  Examples of the fluorosurfactant include trade names “R-08”, “F-472SF”, “R-30”, “BL-20”, “R-61”, “R-90”, “F” -114 "," F-410 "," F-493 "," F-494 "," F-443 "," F-444 "," F-445 "," F-446 "," F-470 " ”,“ F-471 ”,“ F-474 ”,“ F-475 ”,“ F-477 ”,“ F-478 ”,“ F-479 ”,“ F-480SF ”,“ F-482 ”, “F-483”, “F-484”, “F-486”, “F-487”, “F-489”, “F-1720”, “F-178K”, “ESM-1”, “MCF” -350SF "," TF-2066 "," F-472SF "," TF-1366 "," TF-1367 "," F-552 "," F "553", "F-554", "TF-1425", "TF-1437", "TF-1507", "F-1535" (manufactured by DIC Corporation, MegaFuck series); trade name "DFX-18" , "Factent 250", "Factent 251", "FTX-208G", "FTX-218G", "FTX-240G", [FTX-212P], "FTX-220P", "FTX-228P", " FTX-218GL "," FTX-206D "," FTX-218 "," FTX-220D "," FTX-230D "," FTX-240D ", [FTX-750LL]," FTX-730LS "," FTX- 730LM "," FTX-730LL "," FTX-710LL "," FTX-750FM "," FTX-730FS "," FTX-73 "0FM", "FTX-730FL", "Factent 212D", "Factent 710FL", "Factent 730FM", "FTX-209F", "FTX-213F", "FTX-233F", "Futgent 222F" And “Factent 245F” (Neos Co., Ltd. “Factent Series”).

  Among these, trade names “R-08”, “F-472SF”, “R-30”, “F-477”, “F-479”, “TF-1366”, “TF-1367”, “TF” -1425 "(manufactured by DIC Corporation, MegaFuck series); trade names" DFX-18 "," FTX-208G "," FTX-218G "," FTX-240G ", [FTX-212P]," FTX-220P " ”,“ FTX-228P ”,“ FTX-218GL ”“ Factent 710FL ”,“ Factent 730FM ”,“ FTX-209F ”,“ Factent 222F ”,“ Factent 245F ”(manufactured by Neos Co., Ltd.) Series) is preferred.

  Examples of the acrylic surfactant include trade names “Byk-354”, “ByK-358”, and “Byk-361N” (manufactured by BYK Chemie). Among these, a trade name “Byk-361N” (manufactured by Big Chemie) is preferable.

  Examples of the silicone surfactant include trade names “FM-3306”, “FM-3331”, “FM-3321”, “FM-3325”, “FM-4411”, “FM-4421”, “FM”. -4425 "," FM-7711 "," FM-7721 "," FM-7725 "," FM-0411 "," FM-0421 "," FM-0425 "," FM-DA11 "," FM-DA21 " ”,“ FM-DA26 ”,“ FM-0711 ”,“ FM-0721 ”,“ FM-0725 ”,“ TM-0701 ”,“ TM-0701T ”(manufactured by Chisso Corporation); trade name“ Byk- ” 300 "," Byk-306 "," Byk-335 "," Byk-310 "," Byk-341 "," Byk-344 "," Byk-370 "(by Big Chemie) .

  Furthermore, as the silicone-based surfactant, for example, one compound selected from “FM-3306”, “FM-3331”, “FM-3321”, and “FM-3325” and one acid anhydride group described later are used. A reactive organism with a compound having, a compound selected from “FM-3306”, “FM-3331”, “FM-3321” and “FM-3325” and a compound having two or more acid anhydride groups described below Reactive organism with monoamine described later, compound selected from "FM-3306", "FM-3331", "FM-3321" and "FM-3325" and compound having two or more acid anhydride groups described later Reactive organisms, among tetracarboxylic dianhydrides described below, reactive organisms between compounds represented by formula (1-76) and monoamines described below, tetracars described below Among the acid dianhydrides, a reactive product of a compound represented by the formula (1-76) with a diamine described below and a monoamine described below or a tetracarboxylic dianhydride described below with a formula (1-76) An amic acid / imide which is a reactive product of a compound represented by the formula (1) and a diamine described later can be used.

  Among these, trade names “FM-3306”, “FM-3331”, “FM-3321”, “FM-3325”, “FM-4411”, “FM-7711”, “FM-0411”, “FM-” DA11 "," FM-0711 "(manufactured by Chisso Corp.)," FM-3311 "and a reaction product of a compound having one acid anhydride group described below, or" FM-3331 "and acid anhydride described below Amic acid which is a reactive organism between a compound having two or more physical groups and a monoamine described later is preferable.

  Only one type of surfactant may be used, or a mixture of two or more types may be used.

  When a surfactant is used, the content of the surfactant in the inkjet ink is preferably 0.00001% by mass or more and 1.0% by mass or less, and more preferably 0.001% by mass or more with respect to the total mass of the inkjet ink. 1.0 mass% or less is more preferable, 0.01 mass% or more and 1.0 mass% or less are still more preferable. The upper limit of the surfactant content is particularly preferably less than the critical micelle concentration.

  “Critical micelle concentration” refers to the concentration at which the surfactant begins to form micelles in the ink. Therefore, the surfactant does not form micelles in the ink below the critical micelle concentration, and the surfactant forms micelles in the ink when the critical micelle concentration is exceeded.

  When the concentration of the surfactant in the ink reaches the critical micelle concentration, the concentration of the surfactant is increased and the surface tension of the ink hardly decreases. Using this phenomenon, the critical micelle concentration can be determined from the relationship between the surfactant concentration and the surface tension.

  Confirmation that the surfactant in the ink is less than the critical micelle concentration can be confirmed by adding the same kind of surfactant to the ink. That is, if the same kind of surfactant is added to the ink and the surface tension is reduced as compared with that before the addition, the concentration of the surfactant in the ink before the addition is less than the critical micelle concentration. Judgment can be made.

  The critical micelle concentration can be measured by an electric conduction method, a viscosity method, a dye method, a light scattering method, or the like, in addition to the measurement using the surface tension of the ink as described above. Any method can be used, but the method using the surface tension is preferable because it is the most general and simple.

  In addition, as described above, the presence or absence of micelle formation in the ink is measured by adding the same kind of surfactant as the surfactant contained in the ink to the ink and measuring the surface tension before and after the addition of the surfactant. This can be confirmed. That is, if the surface tension of the ink decreases when the surfactant content in the ink is increased by adding the same type of surfactant, the ink before the addition of the same type of surfactant is added. It can be determined that micelles are not formed by the surfactant. In addition to this method, the presence or absence of micelles in the ink should also be confirmed by dynamic light scattering, zeta potential measurement, small-angle neutron scattering, wide-angle X-ray scattering, small-angle X-ray scattering, and transmission electron microscope. Can do.

1.5.7 Examples of pigment pigments include organic pigments and inorganic pigments, and color inks are required to have high color purity, chemical resistance, and heat resistance, and are excellent in color purity, chemical resistance, and heat resistance. Organic pigments are more preferred.

  Examples of the organic pigment include C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment violet 23, C.I. I. Pigment orange 43, C.I. I. Pigment black 1, C.I. I. Pigment pigments such as CI Pigment Black 7, and pigment blue GNH. Only one organic pigment may be used, or two or more organic pigments may be mixed and used.

Examples of inorganic pigments include titanium oxide, titanium black, and carbon black. Only 1 type may be used for an inorganic pigment, and 2 or more types may be mixed and used for it.
A commercial item may be used for the pigment.

  In the case of using a pigment, the content of the pigment in the inkjet ink is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass%, with respect to the total mass of the inkjet ink.

1.5.8 Antistatic agents Antistatic agents can be used to prevent charging. Examples of the antistatic agent include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide; and quaternary ammonium salts.

  Only one type of antistatic agent may be used, or two or more types may be mixed and used.

  The antistatic agent can be used, for example, by being added in the range of 0.01 to 1 part by mass with respect to 100 parts by mass of the inkjet ink excluding the antistatic agent.

1.5.9 Coupling agent Examples of coupling agents include silane coupling agents,
Examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Preferred silane coupling agents include, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, and γ-acryloylpropylmethyldiethoxysilane. Γ-acryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane Run, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-amino Ethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl -Γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxy Examples thereof include silane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyltriethoxysilane.

  Particularly preferable examples of the silane coupling agent include γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane.

  Only 1 type may be used for a coupling agent, and 2 or more types may be mixed and used for it.

  For example, the coupling agent can be added and used in the range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the inkjet ink excluding the coupling agent.

1.5.10 Epoxy curing agent Examples of the epoxy curing agent include organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, polycarboxylic acids, polycarboxylic anhydrides, epoxy resins and amines. Examples include amine adducts obtained by reaction. More specifically, dicyandiamides such as dicyandiamide; adipic acid dihydrazide, organic acid dihydrazides such as 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 2,4-diamino-6- [2′- Imidazolyl- (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, acid anhydrides such as 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, trimellitic acid, and dimer acid. Among these, trimellitic anhydride and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferable.

  Only one type of epoxy curing agent may be used, or two or more types may be mixed and used.

  An epoxy hardening | curing agent can be added and used in 0.2-10 mass parts with respect to 100 mass parts of inkjet ink except an epoxy curing agent, for example.

1.5.11 Curing Agent for Alkenyl-Substituted Nadiimide Examples of the curing agent for alkenyl-substituted nadiimide include azobis-based compounds and acid-generating compounds, with azobis-based compounds being preferred. These curing agents may be used alone or in combination of two or more.

  Examples of the azobis compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and dimethyl-2,2. '-Azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (N -(2-propenyl) -2-methylpropionamide, 2,2′-azobis (N-butyl-2-methylpropionamide), α, α′-azobisisobutyronitrile, among these, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carb Boronitrile) is preferred.

  It is preferable that the ink jet ink of the present invention contains an azobis-based compound together with an alkenyl-substituted nadiimide because there is no tackiness when the coating film is dried and the handling property is excellent.

1.5.12 Examples of dye dyes include organic dyes and inorganic dyes, and color inks are required to have high color purity, chemical resistance, and heat resistance, so that color purity, chemical resistance, and heat resistance are excellent. Organic dyes are more preferred.

  Examples of the organic dye include Disperse Black 9. Only one organic pigment may be used, or two or more organic pigments may be mixed and used.

Examples of inorganic dyes include titanium oxide, titanium black, and carbon black. Only 1 type may be used for an inorganic pigment, and 2 or more types may be mixed and used for it.
A commercial product may be used as the dye.

  When using a dye, the content of the pigment in the inkjet ink is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass%, based on the total mass of the inkjet ink.

1.6. Preparation method of ink-jet ink The ink-jet ink of the present invention uniformly comprises the compound (A), the compound (B) and, if necessary, the compound (B ′), the solvent (C), and other additives. It can be prepared by mixing.

  In addition, the ink-jet ink of the present invention is prepared by using the reaction solution obtained at the time of synthesizing the compound (A) or the compound (B) as it is, the compound (B ′), the solvent (C), other additives, etc. It can also be prepared by uniformly mixing with.

  In the inkjet ink of the present invention, various parameters such as viscosity, surface tension, and boiling point of the solvent can be optimized for inkjet printing. The ink exhibits good ink jet printability (for example, drawability, thick film formation), excellent storage stability, and excellent thermal, electrical, and mechanical properties and excellent adhesion to various substrates. A polyimide film can be formed.

1.7 Inkjet ink viscosity When jetting is performed at room temperature (25 ° C), the inkjet ink of the present invention preferably has a viscosity at room temperature (25 ° C) of 1 to 50 mPa · s, more preferably. Is 5 to 30 mPa · s, more preferably 8 to 20 mPa · s. When the viscosity at the time of discharge 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.

  When jetting by heating the ink head, the viscosity at the heating temperature (preferably 30 to 120 ° C.) of the inkjet ink of the present invention is preferably 1 to 50 mPa · s, more preferably 5 to 5 mPa · s. 30 mPa · s, more preferably 8 to 20 mPa · s. If the viscosity at the heating temperature is less than or equal to the above upper limit value, ink jet ejection defects are unlikely to occur.

1.8 Surface Tension of Inkjet Ink The surface tension of the inkjet ink of the present invention at 25 ° C. is usually 20 to 45 mN / m, preferably 25 to 35 mN / m. When the surface tension is in the above range, good droplets can be formed by jetting and a meniscus can be formed. If the surface tension is too low, the ink spreads immediately after it is ejected from the nozzles of the printer head, and good droplets may not be formed. On the other hand, if the surface tension is too high, it becomes impossible to form a meniscus, which may make ejection impossible.

2. Ink Coating Method, Polyimide Film Manufacturing Method The ink coating method of the present invention includes a step of coating the ink of the present invention by an inkjet coating method to form a coating film (coating film forming process), and heating the coating film. It has the process (heating process) which processes and forms a polyimide film. Here, it is preferable to provide a surface treatment step (surface treatment step) before applying the ink to the substrate, and apply the ink onto the surface-treated substrate to form a coating film.

  Moreover, the manufacturing method of the polyimide film of this invention uses the coating method of the said ink.

2.1 Surface treatment process If necessary, the substrate is surface treated. For the surface treatment, for example, silane coupling agent treatment, UV ozone ashing treatment, plasma treatment, alkali etching treatment, acid etching treatment, and primer treatment are used. Moreover, the board | substrate applicable by this invention is illustrated in the column of the "film substrate, semiconductor wafer, or electronic material board | substrate" mentioned later.

2.2 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 the inkjet ink 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.

  After applying the ink-jet ink of the present invention on a substrate by an ink-jet coating method, the polyamic acid coating film can be formed by drying (removing the solvent) with a hot plate or oven.

  The drying conditions vary depending on the type of ink-containing components and the blending ratio, but are usually 70 to 120 ° C., 5 to 15 minutes when using an oven, and 1 to 5 minutes when using a hot plate.

2.3 Heating Process The heat treatment is performed by, for example, a hot plate or an oven, whereby a polyimide film having a whole surface or a predetermined pattern (for example, a line) is formed. In addition, the formation of the polyimide film is not limited to heat treatment, and treatment such as UV treatment, ion beam, electron beam, gamma ray, and infrared ray may be used.

  After forming the polyamic acid coating film in the coating film forming step, heat treatment is usually performed at 180 to 350 ° C., preferably 180 to 300 ° C., in order to imidize the polyamic acid. The heating time is, for example, 30 to 90 minutes when an oven is used, and 5 to 90 minutes when a hot plate is used. As described above, a polyimide film is formed.

  When the polyamic acid coating film is formed in a pattern, the polyimide film is also formed in a pattern. In this specification, unless otherwise specified, the polyimide film includes a patterned polyimide film.

  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 overwhelmingly small and it is not necessary to use a photomask. For this reason, in the present invention, multi-product mass production is possible, and the number of steps required for production is small.

3 Polyimide film The polyimide film of the present invention is formed by the above-described method for producing a polyimide film. The polyimide film of the present invention has good thermal, electrical and mechanical properties, for example, an insulating film with excellent heat resistance and electrical insulation, excellent adhesion to various substrates, and reliability of electronic components. Yield can be improved.

  In the inkjet ink of the present invention, the solid concentration can be set high as described above. Therefore, in the present invention, a cured film having a thickness of usually 1 μm or more, preferably 1 to 5 μm can be obtained by one ink jetting, and the film thickness is larger than that of a cured film obtained from a conventional ink. . For example, in the case of forming a thick insulating film of about 10 μm, by using the ink of the present invention, the number of overcoating can be reduced as compared with the conventional ink, and the manufacturing process of the insulating film can be shortened.

4 Film Substrate, Semiconductor Wafer or Electronic Material Substrate The film substrate, semiconductor wafer or electronic material substrate of the present invention has the polyimide film described above. Speaking of film substrates, for example, the ink of the present invention is applied to the entire surface or a predetermined pattern (line shape, etc.) by an inkjet coating method on a film substrate such as a polyimide film in which wiring is formed in advance by an inkjet coating method. Then, the film substrate having the polyimide film is obtained by drying and heating the film substrate.

  As a substrate applicable in the present invention, for example, a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, paper that conforms to various standards such as FR-1, FR-3, FR-4, CEM-3, E668, etc. Epoxy substrate, green epoxy substrate, BT resin substrate; substrate made of metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, stainless steel (a substrate having the surface of those metals) 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 (P ZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia), silicon oxide (silica), silicon carbide (silicon carbide), silicon nitride (silicon nitride), boron nitride (boron knight) Ride), substrates made of ceramics such as zinc oxide, mullite, ferrite, steatite, holsterite, spinel, spodumene (may be substrates having the surface of those ceramics); PET (polyethylene terephthalate) resin, PBT ( Polybutylene terephthalate) resin, PCT (polycyclohexylene dimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, poly Substrates made of resins such as polyimide resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic elastomer, and liquid crystal polymer A semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; an electrode such as tin oxide, zinc oxide, ITO (indium tin oxide), or ATO (antimony tin oxide). Examples include a substrate on which a material is formed on a surface; gel sheets such as αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel), and γGEL (gamma gel) (registered trademark of Tyca Corporation).

5 Electronic Component The electronic component of the present invention has the above-described film substrate, semiconductor wafer, or electronic material substrate. Speaking of an electronic component having a film substrate, for example, the ink of the present invention is applied to the entire surface or a predetermined pattern (line shape) by an inkjet coating method on a film substrate such as a polyimide film in which wiring is previously formed by an inkjet coating method. Etc.), and then the film substrate is dried and heated to obtain a flexible electronic component covered with an insulating polyimide film.

6 Illustrative and preferred specific examples of compounds

6.1 Compound having one acid anhydride group One acid anhydride group that can be used for compound (a11) in compound (A) and compound (b3) in compounds (B) and (B ′) described above As a compound which has, the compound represented by a following formula is mentioned, for example.

In the formula, R ²⁰ is a divalent organic group having 2 to 10 carbon atoms in the case of the compound (a11) in the compound (A), and in the case of the compound (b3) in the compounds (B) and (B ′). A divalent organic group having 2 to 98 carbon atoms. R ²⁰ is preferably an organic group having crosslinkability.

Examples of the compound represented by the above formula include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 4-tert-butylphthalic anhydride, 3-fluorophthalic anhydride, 4- Fluorophthalic anhydride, succinic anhydride, glutaric anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, butyl succinic anhydride, n- Compounds having no crosslinkable organic groups, such as octyl succinic anhydride and dodecyl succinic anhydride;
4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, methylcyclohexene-1,2-dicarboxylic anhydride, malee Acid anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, allyl succinic anhydride, 2-buten-1-yl succinic anhydride,
5-norbornene-2,3-dicarboxylic anhydride, allyl nadic anhydride, tetradecenyl succinic anhydride, octadecenyl succinic anhydride, aconitic anhydride, p- (trimethoxysilyl) phenyl succinic anhydride, p -(Triethoxysilyl) phenyl succinic anhydride, m- (trimethoxysilyl) phenyl succinic anhydride, m- (triethoxysilyl) phenyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, triethoxysilyl A compound having a crosslinkable organic group such as propyl succinic anhydride, a compound represented by the formula (α), a compound represented by the formula (β);
Is mentioned.

  The compound represented by the formula (α) can be obtained, for example, by reacting 5-norbornene-2,3-dicarboxylic acid anhydride with trimethoxysilane. The compound represented by the formula (β) can be obtained, for example, by reacting allyl nadic acid anhydride with trimethoxysilane.

  Among the compounds having one acid anhydride group, maleic acid anhydride, citraconic acid anhydride, allyl nadic acid anhydride, 4-ethynylphthalic acid anhydride from the viewpoint of excellent crosslinkability and durability of the resulting coating film 4-phenylethynylphthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimethoxysilylpropyl succinic anhydride, and triethoxysilylpropyl succinic anhydride are preferable.

  Only 1 type may be used for the compound which has one acid anhydride group, and 2 or more types may be mixed and used for it.

6.2 Compound having two or more acid anhydride groups 2 acid anhydride groups that can be used for compound (a12) in compound (A) and compound (b2) in compounds (B) and (B ′) Examples of the compound having two or more include a copolymer of a radical polymerizable monomer having an acid anhydride group and another radical polymerizable monomer, tetracarboxylic dianhydride, and tetracarboxylic dianhydride is preferable. .

  Examples of the copolymer of a radical polymerizable monomer having an acid anhydride group and another radical polymerizable monomer include, for example, styrene-maleic anhydride copolymer, methyl methacrylate-maleic anhydride copolymer, and olefin-anhydride. Mention may be made of maleic acid copolymers and vinyl acetate-maleic anhydride copolymers. Examples of the product include product names SMA1000 and SMA2000 (manufactured by Sartomer).

  As tetracarboxylic dianhydride, the compound represented by a following formula is mentioned, for example.

式中、Ｒ²¹は炭素数２〜１００の四価の有機基であり、但し、化合物（Ａ）における化合物（ａ１２）の場合は炭素数４〜４０の四価の有機基である。

In the formula, R ²¹ is a tetravalent organic group having 2 to 100 carbon atoms, provided that in the case of the compound (a12) in the compound (A), it is a tetravalent organic group having 4 to 40 carbon atoms.

  Examples of the tetracarboxylic dianhydride represented by the above formula include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3. '-Benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic 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 Anhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3 -Dicarboxyphenyl)] hexafluoropropanoic dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), 4, 4 ′-[(isopropylidene) bis (p-phenyleneoxy)] diphthalic dianhydride, ethylenediaminetetraacetic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 3, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene succinic dianhydride And compounds of formula 1-1～1-77 the like.

式（１−７７）中、Ｐｈはフェニル基を表す。

In formula (1-77), Ph represents a phenyl group.

  Among tetracarboxylic dianhydrides, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid dianhydride Anhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropanoic dianhydride, cyclobutane tetracarboxylic dianhydride An anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, and a compound of the formula 1-5 have high solubility in the solvent (C) and high concentration ink Can be adjusted.

  Moreover, high transparency is required depending on the use of the ink for inkjet. In such a case, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4 , 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropanoic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride The product is particularly preferred.

  Only 1 type may be used for the compound which has 2 or more of acid anhydride groups, and 2 or more types may be mixed and used for it.

6.3 Monoamine The monoamine that can be used for the monoamine (b4) in the above-mentioned compound (B ′) is a compound having one amino group, for example, a compound represented by the following formula.

式中、Ｒ²²は炭素数２〜１００の一価の有機基であり、架橋性を持つ有機基であることが好ましい。
上記式で表されるモノアミンとしては、例えば、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルメチルジエトキシシラン、４−アミノブチルトリメトキシシラン、４−アミノブチルトリエトキシシラン、４−アミノブチルメチルジエトキシシラン、ｐ−アミノフェニルトリメトキシシラン、ｐ−アミノフェニルトリエトキシシラン、ｐ−アミノフェニルメチルジメトキシシラン、ｐ−アミノフェニルメチルジエトキシシラン、ｍ−アミノフェニルトリメトキシシラン、ｍ−アミノフェニルメチルジエトキシシラン、２−アミノ安息香酸、３−アミノ安息香酸、４−アミノ安息香酸、２−フルフリルアミン、チラミン、２−（４−アミノフェニル）エチルアミン、ｔｒａｎｓ−４−アミノシクロヘキサノール、モノエタノールアミン、２−アミノエタノール、３−アミノ−１−プロパノール、１−アミノ−２−プロパノール、２−（２−アミノエトキシ）エタノール、５−アミノ−１−ペンタノール、ｎ−ブチルアミン、アニリン、３−エチニルアニリン、４−エチニルアニリン、ペンタフルオロアニリン、トリプトファン、リシン、メチオニン、フェニルアラニン、トレオニン、バリン、イソロイシン、ロイシン、ヒスチジン、アラニン、アルギニン、アスパラギン、セリン、アスパラギン酸、システイン、グルタミン、グルタミン酸、グリシン、プロリン、チロシン、１２−アミノラウリル酸、Ｏ―ホスホリルエタノールアミン、硫化水素２−アミノエチル、２−アミノエタンスルホン酸、４−アミノ桂皮酸、ディスパースブラック９が挙げられる。

In the formula, R ²² is a monovalent organic group having 2 to 100 carbon atoms, and is preferably an organic group having crosslinkability.
Examples of the monoamine represented by the above formula include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-aminobutyltriamine. Methoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldi Ethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylmethyldiethoxysilane, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-furfurylamine, tyramine, 2- (4- Aminoph Nyl) ethylamine, trans-4-aminocyclohexanol, monoethanolamine, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 2- (2-aminoethoxy) ethanol, 5-amino -1-pentanol, n-butylamine, aniline, 3-ethynylaniline, 4-ethynylaniline, pentafluoroaniline, tryptophan, lysine, methionine, phenylalanine, threonine, valine, isoleucine, leucine, histidine, alanine, arginine, asparagine, Serine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, proline, tyrosine, 12-aminolauric acid, O-phosphorylethanolamine, 2-aminoethyl hydrogen sulfide, 2-aminoethane Sulfonic acid, 4-amino-cinnamic acid, Disperse Black 9 and the like.

  Of these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and p-aminophenyltrimethoxysilane are preferred because the ink jetting properties of the resulting ink tend to improve, and 3-aminopropyl is preferred. Triethoxysilane is particularly preferred.

  Only 1 type may be used for monoamine and 2 or more types may be mixed and used for it.

6.4 Diamine The diamine that can be used for the diamine (b1) in the above-mentioned compounds (B) and (B ′) is a compound having two amino groups, for example, a compound represented by the following formula: It is done.

式中、Ｒ²³は炭素数２〜１００の二価の有機基である。

In the formula, R ²³ is a divalent organic group having 2 to 100 carbon atoms.

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

In formula (I), A ¹ is — (CH ₂ ) _m —, where m is an integer of 2 to 12.
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 atom of the cyclohexane ring or the benzene ring may be replaced with —F or —CH ₃ .
Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-3).

式（II）で表される化合物としては、例えば、式（II−１）〜（II−２）で表される化合物が挙げられる。

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

式（III）で表される化合物としては、例えば、式（III−１）〜（III−３）で表される化合物が挙げられる。

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

式（IV）で表される化合物としては、例えば、式（IV−１）〜（IV−５）で表される化合物が挙げられる。

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 diamines, 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-xylylene Range amine, 2,2′-diaminodiphenylpropane, benzidine and 1,1-bis [4- (4-aminobenzyl) phenyl] methane are preferred.

  Examples of diamines further include compounds represented by general formula (VIII).

In formula (VIII), A ⁴ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH—, —N═N— or — (CH ₂ ) _p —, where And p is an integer of 1-6. R ²⁴ 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 ²⁴ may be alkyl having 1 to 30 carbon atoms, and when the positional relationship is meta, R ^{24 24} 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 ²⁴ 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 3rd and 5th positions, or the 2nd and 5th positions, respectively, when the bonding position to the benzene ring of “R ²⁴ —A ⁴ —” is the 1st 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 ²⁵ 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 ²⁶ 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 the formulas (VIII-12) to (VIII-15), R ²⁷ 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 ²⁸ 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 ²⁹ 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 ³⁰ 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-49).

  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 further include compounds represented by formulas (IX) to (X).

In the formulas (IX) and (X), R ³¹ is hydrogen or —CH ₃ , and two R ^32s 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 formula (X), R ³³ and R ³⁴ 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 ³⁴ —) 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 34)}} Ph-a 6 -O- " is considered to be bonded, the steroid nucleus and ^{_{"NH 2 - (R 34 -)}} 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 diamines further include compounds represented by general formulas (XI) and (XII).

In the formula (XI), R ³⁵ 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 ³⁶ is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable. R ³⁷ 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 position or para 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 ³⁸ is hydrogen or alkyl having 1 to 20 carbons.
In formulas (XI-4) to (XI-9), R ³⁹ 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 ⁴⁰ is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable, and R ⁴¹ is hydrogen or having 1 to 30 carbons. Among these, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.

  Further, as the diamine, 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-amino Phenyl) 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, 1,3- Bis (aminomethyl) cyclohexane and neopentyl glycol bis (4-aminophenyl) ether are also mentioned.

  As described above, as the diamine, 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. For example, a naphthalene-based diamine having a naphthalene structure, a fluorene-based diamine having a fluorene structure, a siloxane-based diamine having a siloxane bond, a triazine-based diamine having a triazine skeleton, etc., alone or as a compound having two other amino groups It can be used in admixture with other compounds.

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

In the formula (XIII), R ⁴² and R ⁴³ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁴⁴ is methylene or phenylene optionally substituted by 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. A plurality of R ⁴² , R ⁴³ and R ⁴⁴ may be the same as or different from each other.

  Examples of the diamine further include compounds represented by formulas (XV-1) to (XV-16).

式（ＸＶ−１５）中、ｎは２〜１５の整数である。具体的な製品としてはイハラケミカル社製、エラストマー１０００Ｐ（ｎ（平均値）＝１３．６２）、エラストマー６５０Ｐ（ｎ（平均値）＝８．７６）、エラストマー２５０Ｐ（ｎ（平均値）＝３．２１）が挙げられる。式（ＸＶ−１６）中、ｎは２〜１５の整数、ｍは２〜１５の整数である。具体的な製品としてはイハラケミカル社製、ポレアＳＬ−１００Ａが挙げられる。

In formula (XV-15), n is an integer of 2-15. Specific products are made by Ihara Chemical Co., Ltd., elastomer 1000P (n (average value) = 13.62), elastomer 650P (n (average value) = 8.76), elastomer 250P (n (average value) = 3. 21). In formula (XV-16), n is an integer of 2 to 15, and m is an integer of 2 to 15. As a specific product, there is POLA SL-100A manufactured by Ihara Chemical Co., Ltd.

  In the present invention, preferred examples of the diamine include fluorene diamines represented by the following formulas (4-2-1) to (4-2-3).

  In the present invention, the diamine further includes triazine-based diamines represented by the following formulas (4-3-1), (4-3-2), (4-3-3) and (4-3-4). Is preferred.

Examples of the diamine further include compounds represented by formulas (11) to (30). In formulas (11) to (18), R ⁴⁵ and R ⁴⁶ are each independently alkyl having 3 to 20 carbon atoms.

  The diamine is not limited to the above-exemplified diamines, and various other forms of diamines can be used as long as the object of the present invention is achieved.

  High transparency is required depending on the use of the inkjet ink. In such a case, as the diamine, it is particularly preferable to use 3,3′-diaminodiphenylsulfone and a compound having an integer of y = 1 to 15 in the formula (XIII).

  Only one type of diamine may be used, or two or more types may be mixed and used.

6.5 The mono- or bisalkenyl-substituted nadiimide in the mono- or bisalkenyl-substituted nadiimide compound (B ′) is a compound having one or two alkenyl-substituted nadiimide structures in the molecule, for example, the general formula (B′-1) The alkenyl substituted nadiimide compound represented by these is mentioned.

In formula (B′-1), R ⁴⁷ and R ⁴⁸ 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, and l is 1 or 2.

In formula (B′-1), when l = 1, R ⁴⁹ is hydrogen, alkyl having 1 to 12 carbons, hydroxyalkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 6 carbons. 12 aryl, _{benzyl, - {(C q H 2q} ) O t (C r H 2r O) u C s H 2s X} (q, r and s are each independently an integer of 2 to 6, t is 0 or 1 is an integer, u is an integer of 1 to 30, X is hydrogen or a hydroxyl group),-(R ⁵⁰ ) _a -C ₆ H ₄ -R ⁵¹ (a is 0 or 1 An integer, R ⁵⁰ is alkylene having 1 to 4 carbons, and R ⁵¹ is hydrogen or alkyl having 1 to 4 carbons), —C ₆ H ₄ —TC ₆ H ₅ {T is _{-CH 2 -, - C (CH} 3) 2 -, - CO -, - S- or -SO ₂ - in which} group represented by or these groups, 1-3 hydrogen directly bonded to the aromatic ring is a group which is replaced by a hydroxyl group.

In formula (B′-1), when l = 2, R ⁴⁹ is alkylene having 2 to 20 carbons (any methylene that is not adjacent to each other in alkylene is replaced by —O— or —CH═CH—). Any hydrogen may be replaced by fluorine), cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms,-(R ⁵⁰ ) _a -C ₆ H ₄ -R ^52- (a Is an integer of 0 or 1, and R ⁵⁰ and R ⁵² are each independently alkylene having 1 to 4 carbon atoms), —C ₆ H ₄ —TC ₆ H ₄ —, —C _{6 H 4 -T-C 6 H} 4 -T-C 6 H 4 - or _{-C 6 H 4 -T'-C 6} H 4 -T-C 6 H 4 -T'-C 6 H 4 - {T is a single bond, an alkylene having 1 to 6 carbon _{atoms, -C (CH 3) 2 -} , - C (CF 3) 2 -, - CO -, - O -, - S- or -SO ₂ -, 'Is -CH ₂ - or -O- in which} group represented by or a group 1 to 3 hydrogens directly connected to the aromatic ring is replaced by hydroxyl groups of these groups, the formula (B'-2) Or a group represented by the formula (B′-3).

  In formula (B′-2), a plurality of x's are each independently an integer of 1 to 6, and y is an integer of 1 to 70.

In the formula (B′-1), R ⁴⁷ and R ⁴⁸ are each independently preferably hydrogen or alkyl having 1 to 6 carbons, and when l = 1, R ⁴⁹ is alkyl having 1 to 12 carbons or Preferably, it is aryl having 6 to 12 carbon atoms. When l = 2, R ⁴⁹ is a group represented by — (CH ₂ ) _p — (p is an integer of 6 to 12), a formula (B ′ -4), a group represented by formula (B′-5), a group represented by formula (B′-6), a group represented by formula (B′-2) (provided that x = 3 and y = 1) or a group represented by the formula (B′-3). The ink of the present invention may contain at least two of these alkenyl-substituted nadiimides.

  The alkenyl-substituted nadiimide is, for example, an alkenyl-substituted nadiimide compound obtained by reacting a monoamine or diamine with an alkenyl-substituted nadic acid anhydride represented by the general formula (B′-1 ′).

R ⁴⁷ and R ⁴⁸ in the formula (B'-1 ') has the same meaning as R ⁴⁷ and R ⁴⁸ each formula (B'-1) in.

<Monoalkenyl-substituted nadiimide>
Examples of monoalkenyl-substituted nadiimide compounds in which l is 1 include, for example:
Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, methallylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxy- Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxy-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N-hydroxy-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxy-methallylmethylbicyclo [2.2.1] hept-5-ene- 2, 3 Dicarboximide, N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and these An oligomer is mentioned.

  Also, N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5. -Ene-2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl- Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximi N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide and oligomers thereof.

  N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (2'-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 '-Hydroxyethyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2'-hydroxyethyl) -methallylbicyclo [2.2.1] Hept-5-e 2,3-dicarboximide, and their oligomers are mentioned.

  N- (2 ′, 2′-dimethyl-3′-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 ′, 2 '-Dimethyl-3'-hydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2', 3'-dihydroxypropyl) -allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2 ′, 3′-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (3′-hydroxy-1′-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 ′ -Hydroxy-cyclohexyl - allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and their oligomers are mentioned.

  N- (4′-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4′-hydroxyphenyl) -allylmethylbicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (4′-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N- (4′-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3′-hydroxyphenyl) -allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (3′-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3 -Dikarboki Imido, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2 '-(2'-hydroxyethoxy) ethyl}- Examples include allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and oligomers thereof.

  N- {2 ′-(2′-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2 ′-(2 '-Hydroxyethoxy) ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2'-(2'-hydroxyethoxy) ethyl} -methallyl Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 '-{2'-(2 "-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2. 2.1] Hept-5-ene-2,3-dicarboximide, N- [2 ′-{2 ′-(2 ″ -hydroxyethoxy) ethoxy} ethyl] -allylmethylbicyclo [2.2.1] Hept-5-ene-2,3-di Ruboximide, N- [2 ′-{2 ′-(2 ″ -hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N— {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4 ′-(4′-hydroxy Phenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -meta Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and oligomers thereof are mentioned.

  Only one type of monoalkenyl-substituted nadiimide may be used, or two or more types may be used in combination.

Preferred monoalkenyl substituted nadiimides include
N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide;

  N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylmethyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide , N Cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide;

N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept-5. -Ene-2,3-dicarboximide;
Is mentioned.

  More preferred monoalkenyl-substituted nadiimides include N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1]. Hept-5-ene-2,3-dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide;

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-allylmethyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide ;
Is mentioned.

<Bisalkenyl-substituted nadiimide>
Examples of the bisalkenyl-substituted nadiimide compound in which l is 2 include:
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and oligomers thereof are mentioned.

  In addition, 1,2-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane, 1,2-bis {3 ′-(allyl) Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} Ethyl] ether, bis [2 ′-{3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether, 1,4-bis { 3 ′-(Allylbicyclo [2.2. ] Hept-5-ene-2,3-dicarboximido) propoxy} butane, 1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-di Carboximido) propoxy} butane, and oligomers thereof.

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethyl) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{ (1-Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3 Dicarboximide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene- Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide) and oligomers thereof.

  Also, 2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 ′-{4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 ′-{4 '-(Methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, and these The oligomer of It is.

  Also, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4- Allyl methyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} sulfone, and their oligomers are mentioned.

  Also, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide ) -3,6-dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane, 1,5- Bis {3 '-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2 .1] Hept-5 Ene-2,3-dicarboximide) -2-hydroxy - benzene, and their oligomers are mentioned.

  Also, 1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N, N′-p- (2 -Hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p- (2-hydroxy) xylylene-bis (allylmethylcyclo) [2.2.1] Hept-5-ene-2,3-dicarboximide), N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide), N, N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-p- (2,3 Dihydroxy) xylylene - bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), and these oligomers can be cited.

  Also, 2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2′-hydroxy-phenoxy} phenyl] propane Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximido) -4-hydroxy-phenyl} ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximido) -5-hydroxy-phenyl} sulfone, 1,1,1-tri {4 '-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) } Phenoxymethyl pro Pan, N, N ′, N ″ -tri (ethylenemethallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate, and oligomers thereof.

Moreover, the following compound which has asymmetrical alkylene phenylene group is mentioned.

  Only 1 type may be used for a bis alkenyl substituted nadiimide, and 2 or more types may be mixed and used for it.

Preferred bisalkenyl substituted nadiimides include
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide);

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide), 2,2-bis [4 '-{4'-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenoxy} phenyl ] Propane, 2,2-bis [4 ′-{4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2 -Bis [4 '-{4'-(Meta Rubicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane;

  Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4 -(Ant Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} sulfone;

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone;
Is mentioned.

More preferred bisalkenyl substituted nadiimides include
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (allylmethylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide), N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide), N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide), N, N′-dodecamethylene-bis (a) Rilbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-cyclohexylene- Bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide);

  N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-p-phenylene-bis (allylmethylbicyclo [ 2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N ′-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-xylylene-bis (allylbicyclo) [2.2.1] Hept-5-ene-2,3-dica Boxoxyimide), N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis ( Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximide);

  2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 '-{4'-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 '-{4'- (Methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene -2,3-dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane;

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept -5-ene-2,3-dicarboximido) phenyl} methane;
Is mentioned.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. The names of components used in Examples and Comparative Examples are indicated by abbreviations. This abbreviation is used in the following description.

ＦＭ３３１１：「ＦＭ−３３１１」（チッソ（株）製） Raw material EtOH: ethanol ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride BAPP: 2,2-bis [4- , compound (A), compound (B), compound (B ′), etc. (4-Aminophenoxy) phenyl] propane DDS: 3,3-diaminodiphenylsulfone 4-EPA: 4-ethynylphthalic anhydride MA: maleic anhydride CA: citraconic anhydride APSE: 3-aminopropyltriethoxysilane SMA1000: a compound represented by the following formula

FM3311: “FM-3331” (manufactured by Chisso Corporation)

Compound (A)
EtODPA: a compound represented by the following formula

  EtOH (100.63 g) and ODPA (1.09 g) were added to the reaction vessel, and the mixture was stirred in a water bath at 40 ° C. for 12 hours. The reaction solution after the reaction was concentrated under reduced pressure to obtain a solid material consisting of EtODPA.

Compound (A)
EtSMA1000: a compound represented by the following formula

  EtOH (100.21 g) and SMA1000 (1.01 g) were added to the reaction vessel and stirred in a water bath at 40 ° C. for 72 hours. The reaction solution after the reaction was concentrated under reduced pressure to obtain a solid consisting of EtSMA1000.

Solvent (C)
EDM: Diethylene glycol methyl ethyl ether GBL: γ-butyrolactone

Surfactant FM3311 / MA: Amic acid solution obtained by reacting FM3311 and MA in EDM at a molar ratio (FM-3311: MA) = 1: 2 so that the solid content is 20% by weight.

Method for Measuring Weight Average Molecular Weight Mw of compounds (B) and (B ′) can be measured by gel permeation chromatography (GPC). Specifically, it is diluted with dimethylformamide (DMF) so that the solid content concentration of the compound (B) or the compound (B ′) is about 1% by mass, and as a GPC device, JASCO GULLIVER, manufactured by JASCO Corporation. Using 1500 (intelligent differential refractometer RI-1530), Tosoh Co., Ltd. column G4000HXL, G3000HXL, G2500HXL and G2000HXL are connected in this order, and the measurement conditions are the column temperature The temperature is 40 ° C. and the flow rate is 1.0 ml / min. Under the above conditions, Mw can be determined by using the obtained diluted solution as a developing agent, measuring by GPC method, and converting to polystyrene.

[Preparation of inkjet ink]
[Example 1]
A reaction vessel was charged with BAPP (0.80305 g, 1.96 mmol), ODPA (0.30345 g, 0.98 mmol) and EtODPA (0.39355 g, 0.98 mmol), and EDM (1.75 g) and GBL ( 1.75 g) was added and stirred at room temperature for 2 hours. As shown in the following reaction formula (1), the reaction of BAPP and ODPA proceeded to obtain a reaction solution containing EtODPA as compound (A) and a reaction adduct of BAPP and ODPA as compound (B). The reaction solution after the reaction was designated as inkjet ink (1). The solid content concentration of the ink (1) was 30% by mass, and the viscosity was 62.0 mPa · s. The apparent weight average molecular weight of the ink (1) was 2,383.

  EDM (0.75 g), GBL (0.75 g) and FM3311 / MA (0.00675 g) were added to 3 g of ink (1) to obtain an inkjet ink (1 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (1 ′) was 13.7 mPa · s.

[Example 2]
In a reaction vessel, BAPP (4.7653 g, 11.6 mmol), ODPA (0.9003 g, 2.90 mmol), EtODPA (2.3353 g, 5.81 mmol) and 4-EPA (0.99991 g, 5.81 mmol) were added. The EDM (10.5g) and GBL (10.5g) were added as a solvent, and it stirred at room temperature for 2 hours. As shown in the following reaction formula, the reaction of BAPP, ODPA and 4-EPA proceeds, EtODPA as compound (A), the reaction adduct of BAPP and ODPA as compound (B), and compounds (B) and (B ′). A reaction solution containing a reaction adduct of BAPP, ODPA and 4-EPA and a reaction adduct of BAPP and 4-EPA was obtained. The reaction solution after the reaction was designated as inkjet ink (2). The solid content concentration of the ink (2) was 30% by mass, and the viscosity was 32.3 mPa · s. The apparent weight average molecular weight of the ink (2) was 1,307.

  EDM (0.3 g), GBL (0.3 g), and FM3311 / MA (0.0054 g) were added to 3 g of ink (2) to obtain an inkjet ink (2 ′) having a solid content concentration of 25 mass%. . The viscosity of the ink (2 ′) was 18.2 mPa · s.

[Example 3]
A reaction vessel was charged with BAPP (1.390 g, 3.39 mmol), ODPA (0.2626 g), EtODPA (0.6812 g, 1.69 mmol) and MA (0.1660 g, 1.69 mmol), and EDM ( 3.75 g) and GBL (3.75 g) were added and stirred at room temperature for 2 hours. As shown in the following reaction formula, the reaction of BAPP, ODPA and MA proceeds, EtODPA as compound (A), BAPP and ODPA reaction adduct as compound (B), BAPP as compounds (B) and (B ′), A reaction solution containing a reaction adduct of ODPA and MA and a reaction adduct of BAPP and MA was obtained. FM3311 / MA (0.015 g) was added to the reaction solution after the reaction to prepare an inkjet ink (3). The solid content concentration of the ink (3) was 25% by mass, the viscosity was 12.2 mPa · s, and the apparent weight average molecular weight of the ink (3) was 1,185.

[Example 4]
A reaction vessel was charged with CA (8.069 g, 71.99 mmol) and APSE (15.938 g, 71.99 mmol), EDM (6.001 g) was added as a solvent, and the mixture was refluxed at 180 ° C. for 3 hours (the following reaction). See formula). Into a new reaction vessel, the reaction solution after reaction (3.7667 g) and the ink jet ink (1) obtained in Example 1 (1.9980 g) were charged, EDM (1.4552 g) as a solvent, surfactant As a result, FM3311 / MA (0.0052 g) was added to obtain an inkjet ink (4). The solid content concentration of the ink (4) was 50% by mass, and the viscosity was 13.8 mPa · s.

[Example 5]
A reaction vessel was charged with BAPP (1.5424 g, 3.76 mmol), ODPA (0.5828 g, 1.88 mmol) and EtSMA1000 (0.8748 g, 0.16 mmol), with EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as shown in the above reaction formula (1) to obtain a reaction solution containing EtSMA1000 as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B). The reaction solution after the reaction was designated as inkjet ink (5). The solid content concentration of the ink (5) was 30% by mass, and the viscosity was 120.0 mPa · s.

  EDM (0.75 g), GBL (0.75 g) and FM3311 / MA (0.00675 g) were added to 3 g of ink (5) to obtain an inkjet ink (5 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (5 ') was 18.0 mPa · s.

[Example 6]
A reaction vessel was charged with BAPP (1.6493 g, 4.018 mmol), ODPA (0.6232 g, 2.008 mmol) and EtODPA (0.7275 g, 1.809 mmol), with EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as in the above reaction formula (1), and a reaction solution containing EtODPA as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B) was obtained. The reaction solution after the reaction was used as inkjet ink (6). The solid content concentration of the ink (6) was 30% by mass, and the viscosity was 66.4 mPa · s. The apparent weight average molecular weight of the ink (6) was 2,120.

  EDM (0.75 g), GBL (0.75 g) and FM3311 / MA (0.00675 g) were added to 3 g of ink (6) to obtain an inkjet ink (6 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (6 ′) was 16.5 mPa · s.

[Example 7]
A reaction vessel was charged with BAPP (1.5610 g, 3.803 mmol), ODPA (0.5898 g, 1.901 mmol) and EtODPA (0.8491 g, 2.110 mmol), and EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as in the above reaction formula (1), and a reaction solution containing EtODPA as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B) was obtained. The reaction solution after the reaction was used as an inkjet ink (7). The solid content concentration of the ink (7) was 30% by mass, and the viscosity was 56.0 mPa · s. The apparent weight average molecular weight of the ink (7) was 2,083.

  EDM (0.75 g), GBL (0.75 g) and FM3311 / MA (0.00675 g) were added to 3 g of the ink (7) to obtain an inkjet ink (7 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (7 ') was 12.4 mPa · s.

[Comparative Example 1]
A reaction vessel was charged with ODPA (1.3644 g, 4.40 mmol), DDS (0.2576 g, 1.04 mmol) and APSE (1.3780 g, 6.22 mmol), and EDM (3.5 g), GBL ( 3.5 g) and FM3311 / MA (0.015 g) were added to obtain an inkjet ink (C1). The ink (C1) had a solid content concentration of 30% by mass and a viscosity of 13.0 mPa · s.

[Comparative Example 2]
ODPA (3.88738 g, 12.49 mmol), BAPP (5.1262 g, 12.49 mmol) were charged into a reaction vessel, and EDM (10.5 g) and GBL (10.5 g) were added as solvents, and an inkjet ink was added. (C2) was obtained. The solid content concentration of the ink (C2) was 30% by mass, the viscosity was very high, and measurement was impossible.

[Comparative Example 3]
ODPA (1.5495 g, 4.99 mmol), BAPP (2.0505 g, 4.99 mmol) were charged into a reaction vessel, EDM (13.2 g) and GBL (13.2 g) were added as solvents, and an ink jet ink was added. (C3) was obtained. The ink (C3) had a solid content concentration of 12% by mass and a viscosity of 3855 mPa · s.

[Comparative Example 4]
A reaction vessel was charged with BAPP (1.7188 g, 4.187 mmol), ODPA (0.6494 g, 2.009 mmol) and EtODPA (0.6317 g, 1.570 mmol), and EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as in the above reaction formula (1), and a reaction solution containing EtODPA as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B) was obtained. The reaction solution after the reaction was designated as inkjet ink (C4). The ink (C4) had a solid content concentration of 30% by mass and a viscosity of 67.5 mPa · s. The apparent weight average molecular weight of the ink (C4) was 2,256.

  EDM (0.75 g), GBL (0.75 g), and FM3311 / MA (0.00675 g) were added to 3 g of ink (C4) to obtain an inkjet ink (C4 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (C4 ′) was 18.2 mPa · s.

[Comparative Example 5]
A reaction vessel was charged with BAPP (1.4781 g, 3.601 mmol), ODPA (0.5585 g, 1.800 mmol) and EtODPA (0.9634 g, 2.394 mmol), with EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as in the above reaction formula (1), and a reaction solution containing EtODPA as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B) was obtained. The reaction solution after the reaction was used as an inkjet ink (C5). The solid content concentration of the ink (C5) was 30% by mass, and the viscosity was 78.0 mPa · s. The apparent weight average molecular weight of the ink (C5) was 2,048.

  EDM (0.75 g), GBL (0.75 g), and FM3311 / MA (0.00675 g) were added to 3 g of ink (C5) to obtain an inkjet ink (C5 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (C5 ′) was 20.1 mPa · s.

[Comparative Example 6]
A reaction vessel was charged with BAPP (1.8486 g, 4.503 mmol), ODPA (0.6985 g, 2.252 mmol) and EtODPA (0.453 g, 1.126 mmol), with EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as in the above reaction formula (1), and a reaction solution containing EtODPA as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B) was obtained. The reaction solution after the reaction was designated as inkjet ink (C6). The ink (C6) had a solid content concentration of 30% by mass and a viscosity of 49.8 mPa · s. The apparent weight average molecular weight of the ink (C6) was 2,389.

  EDM (0.75 g), GBL (0.75 g), and FM3311 / MA (0.00675 g) were added to 3 g of ink (C6) to obtain an inkjet ink (C6 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (C6 ′) was 12.4 mPa · s.

[Comparative Example 7]
A reaction vessel was charged with BAPP (1.2723 g, 3.099 mmol), ODPA (0.4807 g, 1.550 mmol) and EtODPA (1.247 g, 3.099 mmol), with EDM (3.5 g) and GBL ( 3.5 g) was added and stirred at room temperature for 2 hours. The reaction of BAPP and ODPA progressed as in the above reaction formula (1), and a reaction solution containing EtODPA as the compound (A) and a reaction adduct of BAPP and ODPA as the compound (B) was obtained. The reaction solution after the reaction was designated as inkjet ink (C7). The solid content concentration of the ink (C7) was 30% by mass, and the viscosity was 37.2 mPa · s. The apparent weight average molecular weight of the ink (C7) was 2,173.

  EDM (0.75 g), GBL (0.75 g), and FM3311 / MA (0.00675 g) were added to 3 g of ink (C7) to obtain an inkjet ink (C7 ′) having a solid content concentration of 20 mass%. . The viscosity of the ink (C7 ′) was 11.0 mPa · s.

[Formation of polyimide film]
As a coating apparatus, an inkjet coating apparatus DMP-2831 (manufactured by FUJIFILM Dimatix) was used. The coating conditions were set to 1 dot width and a dot pitch of 25 μm, the heater of the inkjet head was set to 30 ° C., the piezoelectric voltage was set to 20 V, and the drive frequency was set to 5 kHz. Under the above conditions, a line having a length of 5 cm was applied to a 1.5 mm thick glass substrate at room temperature (25 ° C.) using the inks obtained in Examples and Comparative Examples.

  In [Examples 1 to 3, 5 to 7] and [Comparative Examples 1 to 7], the substrate after application was dried for 5 minutes on a hot plate at 80 ° C., and then heated in an oven at 300 ° C. for 60 minutes, An insulating polyimide film formed in a shape was obtained. In [Example 4], the coated substrate was dried on an 80 ° C. hot plate for 5 minutes and then heated in an oven at 180 ° C. for 60 minutes to obtain a polyimide film.

  The characteristics of the obtained ink and polyimide film were evaluated as follows. Unless otherwise specified, the ink-jet inks obtained in the examples and comparative examples are simply referred to as “ink” below.

  For example, in Example 1, the line width of the polyimide film was 60 μm, the edge linearity was good without being jagged, and the film thickness of the line was 1.2 μm. In addition to the results of Example 1, other results are also shown in Tables 1 and 2.

(I) Viscosity The viscosity of the ink was measured at 25 ° C. using an E-type viscometer (VISCONIC ELD manufactured by TOKYO KEIKI).

(Ii) Weight average molecular weight The apparent weight average molecular weight of the ink was measured as follows. The ink was diluted with dimethylformamide (DMF) so that the solid content concentration was about 1% by mass. As a GPC apparatus, JASCO GULLIVER 1500 (intelligent differential refractometer RI-1530) manufactured by JASCO Corporation was used. As the column, a column formed by connecting four columns of Tosoh Corporation columns G4000HXL, G3000HXL, G2500HXL, and G2000HXL in this order was used. The measurement conditions were a column temperature of 40 ° C. and a flow rate of 1.0 ml / min. Under the above conditions, the obtained diluted solution was used as a developing agent, measured by GPC method, and converted to polystyrene to obtain the weight average molecular weight. The apparent weight average molecular weight of the ink is a measure of the weight average molecular weight of the compounds (B) and (B ′).

(Iii) Line width and edge linearity of polyimide film The line width and edge linearity of the polyimide film were observed using an optical microscope.

(Iv) Film thickness of polyimide film line For measuring the film thickness of the polyimide film, a stylus type step gauge XP-200 (manufactured by Ambios Technology) was used. The measurement results at three locations were averaged to obtain the film thickness of the polyimide film line.

(V) Volume resistivity, dielectric constant and withstand voltage (electrical characteristics)
Ink was applied onto the chromium substrate by spin coating, and dried at 80 ° C. for 5 minutes. Further, the substrate was put in an oven and heated at 300 ° C. for 30 minutes in [Examples 1-3, 5-7] and [Comparative Examples 1-7] and at 60 ° C. for 60 minutes in [Example 4] to form a film. A polyimide film having a thickness of about 2 μm was formed. Then, aluminum was vapor-deposited on the polyimide film, and the electrode was created.
The dielectric constant was measured using a precision LCR meter E4980A (manufactured by Agilent Technologies). Volume resistivity and withstand voltage were measured using a digital super insulation / microammeter DSM-8104 (manufactured by Hioki Electric Co., Ltd.).

(Vi) Linear expansion coefficient (thermal characteristics)
The ink was applied onto a substrate (aluminum foil) using an applicator, and dried at 80 ° C. for 5 minutes using a hot plate. Further, the substrate was put in an oven, and in [Examples 1-3, 5-7] and [Comparative Examples 1-7], heated at 300 ° C. for 30 minutes, and in [Example 4], heated at 180 ° C. for 60 minutes. A polyimide film was formed on one side of the substrate. In addition, the obtained polyimide film was fragile, and the test piece was not obtained. After peeling the polyimide film from the base material, the thermal linear expansion coefficient was measured using a heat / stress / strain measuring device (manufactured by SII Nanotechnology, TMA / SS6100).
The measurement conditions are shown below.
Sample length: 10mm
Sample width: 3mm
Temperature rise start temperature: 30 ° C
Temperature rise end temperature: 300 ° C
Temperature increase rate: 10 ° C / min
Atmosphere: In air Calculation of linear expansion coefficient: 50 to 125 ° C (first scan)

(Vii) 5% weight loss temperature (thermal properties)
The 5% weight loss temperature was measured using a sample piece for measuring the linear expansion coefficient and a differential thermogravimetric simultaneous measurement apparatus (manufactured by Seiko Instruments Inc., SSC 5200).

The measurement conditions are shown below.
Temperature rise start temperature: 30 ° C
Temperature rise end temperature: 500 ° C
Temperature increase rate: 10 ° C / min
Atmosphere: in the air

(Viii) Elastic modulus and breaking strength of polyimide film (mechanical properties)
A polyimide film used for the test was formed by the same method as (vi) linear expansion coefficient (thermal characteristics). When the obtained polyimide film was fragile and a test piece could not be obtained, measurement was impossible. A static material tester EZGraph (manufactured by Shimadzu Corporation) was used for measuring the elastic modulus and breaking strength of the polyimide film. The measurement results of three times were averaged to obtain the elastic modulus and breaking strength of the polyimide film.

(Ix) 180 ° peel strength of polyimide film (mechanical properties)
Ink was printed on an aluminum substrate using an ink jet device and dried at 80 ° C. for 5 minutes. Further, the substrate was put in an oven and heated at 300 ° C. for 30 minutes in [Examples 1-3, 5-7] and [Comparative Examples 1-7] and at 60 ° C. for 60 minutes in [Example 4] to form a film. A polyimide film having a thickness of about 2 μm was formed. For the measurement of peel strength, a static material testing machine EZGraph (manufactured by Shimadzu Corporation) was used. The force applied when the aluminum substrate was peeled off from the obtained polyimide film was measured. In addition, the obtained polyimide film was fragile, and the test piece was not obtained. The results of three measurements were averaged to calculate the peel strength.
The evaluation results of the above examples and comparative examples are shown in Tables 1 and 2.

  Examples of methods for utilizing the polyimide film obtained from the ink jet ink of the present invention include an insulating film for a flexible wiring board, an insulating film for a semiconductor element, and an electronic component having them.

Claims (17)

(A) a compound represented by the general formula (1) (hereinafter also referred to as “compound (A)”);
(B) an ink containing a compound represented by the general formula (2) (hereinafter also referred to as “compound (B)”),
When the total number of moles of the combination of —COOR ² and —COOR ³ of the compound (A) contained in the ink is α and the total number of moles of —NH—R ⁵ of the compound (B) is β, α And β satisfy the formula (I): 0.75 <α / β <1.33,
Thermosetting inkjet ink.

[In Formula (1), n is an integer greater than or equal to 1,
When n = 1, R ¹ is a divalent organic group having 2 to 10 carbon atoms,
When n = 2, R ¹ is a tetravalent organic group having 4 to 40 carbon atoms,
When n = 3, R ¹ is a hexavalent organic group having 6 to 60 carbon atoms,
When n ≧ 4, R ¹ is a 2 × n-valent organic group having 2 to 30 carbon atoms,
R ² is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and may be the same or different when a plurality of R ² are present, and R ³ is hydrogen or trimethylsilyl. It may be the same or different. ]

[In the formula (2), R ⁴ is a group represented by the general formula (3) or (4), R ⁵ is hydrogen or a monovalent detachable organic group having 1 to 100 carbon atoms, R ⁵ ′ is a group represented by —NH—R ⁵ or —NH—CO—R ⁶ —COOH (R ⁶ is a divalent organic group having 2 to 98 carbon atoms). ]

[In the formulas (3) and (4), R ⁷ is a divalent organic group having 2 to 100 carbon atoms, and when a plurality of R ⁷ are present, they may be the same or different, and R ⁸ has 2 to 100 carbon atoms. It is a tetravalent organic group, and when there are a plurality thereof, they may be the same or different, and m is an integer of 0 to 1000. ] The thermosetting inkjet ink according to claim 1, wherein the ink further comprises (B ′) at least one selected from compounds represented by general formulas (5) to (9).

[In the formula (5), a plurality of R ⁶ are each independently a divalent organic group having 2 to 98 carbon atoms, and R ⁷ is a divalent organic group having 2 to 100 carbon atoms. May be the same or different, R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and when there are a plurality thereof, they may be the same or different, and n is an integer of 0 to 1000. ]

[In the formulas (6) and (7), a plurality of R ⁶ are each independently a divalent organic group having 2 to 98 carbon atoms, and R ⁷ is a divalent organic group having 2 to 100 carbon atoms, When present in plural, they may be the same or different, R ⁸ is a tetravalent organic group having 2 to 100 carbon atoms, and when present in plural, they may be the same or different, and n is an integer of 1 to 1000 And m is an integer from 0 to 1000. ]

[In formulas (8) and (9), R ⁶ is a divalent organic group having 2 to 98 carbon atoms, and R ⁹ is a monovalent organic group having 2 to 100 carbon atoms. ] In the formula (1), n is 2, R ¹ is a tetravalent organic group having 4 to 40 carbon atoms,
In the formula (2), R ⁵ is hydrogen.
The thermosetting ink jet ink according to claim 1. R ¹ in the formula (1) is a residue of tetracarboxylic dianhydride,
R ⁸ in the above formulas (3) to (4) is a residue of tetracarboxylic dianhydride,
The thermosetting inkjet ink according to claim 3. Further comprising a solvent (C),
The thermosetting inkjet ink according to any one of claims 1 to 4.   Solvent (C) is ethyl lactate, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl butyl ether, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol Monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl It is a solvent containing one or more selected from ether, and the group consisting of γ- butyrolactone, thermally curable inkjet ink according to claim 5. Further comprising an epoxy resin,
The thermosetting inkjet ink according to any one of claims 1 to 6. The epoxy resin is N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetra. The thermosetting inkjet ink according to claim 7, which is one or more compounds selected from the group consisting of glycidyl-4,4'-diaminodiphenylmethane and compounds represented by formulas (D1) to (D5).

[In the formulas (D4) and (D5), n is an integer of 0 to 20. ] A surfactant is further included in the range of 0.00001% by mass to 1.0% by mass,
The thermosetting inkjet ink according to any one of claims 1 to 8. And further comprising at least one alkenyl-substituted nadiimide compound selected from a trisalkenyl-substituted nadiimide compound and a tetraalkenyl-substituted nadiimide compound,
The thermosetting inkjet ink according to any one of claims 1 to 9. Further comprising a pigment,
The thermosetting inkjet ink according to any one of claims 1 to 10. An ink comprising: a step of applying the ink-jet ink according to any one of claims 1 to 11 by an ink-jet coating method to form a coating film; and a step of heat-treating the coating film to form a polyimide film. Application method. A step of surface-treating the substrate,
Applying the inkjet ink according to any one of claims 1 to 11 by an inkjet coating method on the surface-treated substrate to form a coating film; and heating the coating film. An ink application method comprising a step of forming a polyimide film.   The manufacturing method of a polyimide film using the coating method of the ink of Claim 12 or 13.   A polyimide film formed by the manufacturing method according to claim 14.   A film substrate, a semiconductor wafer, or an electronic material substrate having a polyimide film formed by the production method according to claim 14.   An electronic component comprising the film substrate, the semiconductor wafer, or the electronic material substrate according to claim 16.