JP5569216B2 - Thermosetting composition and use thereof - Google Patents

Description

  The present invention relates to a thermosetting composition and use thereof. More specifically, a thermosetting composition containing a specific compound, an ink jet ink comprising the composition (the ink is used for forming an insulating film, for example, in the manufacture of electronic components), and the ink. The present invention relates to a cured film, a method for applying the ink, a method for forming a cured film, a substrate with a cured film having the cured film, and an electronic component having the substrate.

Polyimide is widely used in the field of electronic communication because it is excellent in heat resistance and electrical insulation (see, for example, Patent Documents 1 to 3). In the case of using polyimide as a desired pattern film, conventionally, a method of forming a pattern using etching or photosensitive polyimide has been generally used. However, the formation of the pattern requires a large amount of chemicals such as a photoresist, a developer, an etching solution, a stripping solution, and a complicated process. Therefore, in recent years, a method of forming a desired polyimide pattern film by inkjet has been studied.
Various ink-jet inks have been proposed (for example, see Patent Documents 4 to 5), but various parameters such as ink viscosity and solvent boiling point are not optimized in order to eject and print as ink-jet ink. must not.
Regarding the viscosity, generally, it is required to have a low viscosity of about 1 to 50 mPa · s at the discharge temperature (the temperature of the ink at the time of discharge). In particular, in the case of piezo-type ink jet printing, since the discharge pressure of the piezoelectric element is small, if the viscosity increases, ink cannot be discharged in some cases.

The boiling point of the solvent is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. If the boiling point is too low, the solvent in the ink at the nozzle portion of the printer head will evaporate particularly when the ink is heated and ejected. As a result, the viscosity of the ink changes, and the ink cannot be ejected or the ink components may solidify. On the other hand, if the boiling point is too high, the drying of the ink after printing is too slow and the printing pattern may be deteriorated.
Various inks containing polyimide or polyamic acid that becomes polyimide by heat treatment have been proposed as polyimide ink-jet inks (see, for example, Patent Documents 6 to 10).

  In addition to the necessary properties such as the viscosity and the boiling point of the solvent, the polyimide-based inkjet ink has important functions and properties as a polyimide film when the film is formed. For example, for polyimide films, electrical properties such as volume resistivity and insulation; mechanical properties such as bending test, elastic modulus and tensile elongation; alkali resistance properties; thermal properties such as thermal decomposition temperature and thermal linear expansion coefficient Various characteristics such as are required. Furthermore, secondary problems such as adhesion between the polyimide film and the substrate, problems of warping of the substrate due to shrinkage during film formation, and migration resistance are also cited.

Originally, polyimide has been widely used for electronic materials as an excellent resin with the above properties, but due to limitations in designing materials for ink-jet ink, the functions and properties of the polyimide film are well balanced and fully expressed. It was extremely difficult to do.
The functions and properties of the polyimide film vary depending on the application. In particular, in a flexible printed wiring board application using a film substrate and a semiconductor application using a silicon wafer substrate, adhesion between the substrate and the polyimide film is a major issue.

Methods for controlling the functions and properties of the polyimide film include: a method for optimizing the structure of the starting tetracarboxylic acid derivative and diamine derivative; a method for optimizing the structure of the polymer such as copolymerization and polymer blending; a polyimide precursor Various methods such as adjustment of the imidization ratio of the resin; addition of a crosslinking agent and the like have been studied.
Specific examples of optimizing the structure of the raw material tetracarboxylic acid derivative to express the functions and characteristics of the polyimide film include phosphorus-containing polyesterimide precursors produced using tetracarboxylic acid anhydrides with a specific structure and It has been disclosed that even if the phosphorus polyesterimide is thinned, it retains the same flame retardance as before and has good thermal diffusivity (see, for example, Patent Document 11). However, Patent Document 11 does not disclose any adhesiveness between the substrate and the polyimide film, and does not take into consideration necessary characteristics such as the viscosity of the ink-jet ink and the boiling point of the solvent.

JP 2000-039714 A JP 2003-238683 A JP 2004-094118 A JP 2003-213165 A JP 2006-131730 A JP 2009-35700 A International Publication No. 2008/123190 Pamphlet JP 2009-144138 A International Publication No. 2008/059986 Pamphlet JP 2009-203440 A JP 2009-221309 A

  The present invention includes (1) a thermosetting composition capable of forming a cured film showing good adhesion to a substrate, for example, for printed wiring board use or semiconductor use, (2) viscosity, boiling point of solvent, etc. Various parameters optimized for inkjet printing, thermosetting composition showing good inkjet printability and excellent storage stability, (3) relatively thick cured film (more than 2μm) by one jetting (4) Thermosetting composition having good electrical characteristics, alkali resistance characteristics and thermal characteristics and capable of forming a cured film with a small amount of warping The purpose is to provide.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using the following thermosetting composition, and the present invention has been completed. That is, the present invention is as follows.

［式（１）中、Ｚは二価の有機基である。］
［２］ 酸無水物（ａ２）および（ａ２’）が、それぞれ独立に、ジカルボン酸無水物およびテトラカルボン酸二無水物から選ばれる少なくとも１種である、前記［１］項に記載の熱硬化性組成物。
［３］
ジカルボン酸無水物が、一般式（２）で表される化合物であり、
テトラカルボン酸二無水物が、一般式（３）で表される化合物である、
前記［２］項に記載の熱硬化性組成物。

［式（２）中、Ｘは、

の何れかであり、
式（３）中、Ｙは、

の何れかである｛ここで、Ｒ¹は、単結合、―Ｏ―、―ＣＯ―、―ＳＯ₂―、―ＣＨ₂―、―Ｃ（ＣＨ₃）₂―、―Ｃ（ＣＦ₃）₂―、

の何れかであり、Ｒ²は、単結合、―Ｏ―、―ＣＯ―、―ＳＯ₂―、―ＣＨ₂―、―Ｃ（ＣＨ₃）₂―、―Ｃ（ＣＦ₃）₂―の何れかである。｝。］
［４］ カルボキシル基含有化合物（Ａ）が、一般式（ｉ−１）〜（ｉ−３）、（ii−１）〜（ii−８）で表される化合物から選ばれる少なくとも１種である、前記［３］項に記載の熱硬化性組成物。

［式（ｉ−１）〜（ｉ−３）、（ii−１）〜（ii−８）中、Ｘは式（２）中のＸと同義であり、Ｙは式（３）中のＹと同義であり、Ｚは式（１）のＺと同義であり、―ＣＯ―Ａ―ＣＯＯＨは式（２）または式（３）で表される化合物の残基である。］
［５］ 一般式（１）中のＺが、炭素数１〜２０のアルキレン、前記アルキレン中の任意のメチレンを芳香族基に置き換えた基、または−（ＣＨ₂ＣＨ₂−Ｏ）_n−ＣＨ₂ＣＨ₂−で表される基（ｎは１〜１０の整数）である、前記［１］〜［４］の何れか一項に記載の熱硬化性組成物。
［６］ エポキシ化合物（Ｂ）が、アルキレングリコールジグリシジルエーテル、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、テトラフェノールエタン型エポキシ樹脂、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（Ｂ１）〜（Ｂ４）で表される化合物からなる群より選ばれる少なくとも１種の化合物である、前記［１］〜［５］の何れか一項に記載の熱硬化性組成物。

［式（Ｂ１）中、ｐは１〜５０の整数である。］
［７］ 溶媒（Ｃ）をさらに含有する、前記［１］〜［６］の何れか一項に記載の熱硬化性組成物。
［８］ 溶媒（Ｃ）が、乳酸エチル、エタノール、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、１，３−ジオキソラン、エチレングリコールジメチルエーテル、１，４−ジオキサン、プロピレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート、アニソール、エチルラクテート、ジエチレングリコールジメチルエーテル、ジプロピ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イソプロピルメチルエーテル、ジプロピレングリコールモノメチルエーテル、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モノメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリプロピ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、ジ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フェニルエーテル、トリエチレングリコールモノメチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、トリエチレングリコールジビニルエーテル、トリプロピレングリコールモノメチルエーテル、テトラメチレングリコールモノビニルエーテル、安息香酸メチル、安息香酸エチル、１−ビニル−２−ピロリドン、１−ブチル−２−ピロリドン、１−エチル−２−ピロリドン、１−（２−ヒドロキシエチル）−２−ピロリドン、２−ピロリドン、Ｎ−メチル−２−ピロリドン、１−アセチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジメチルプロピオンアミド、Ｎ−メチル−ε−カプロラクタム、１，３−ジメチル−２−イミダゾリジノンおよびγ−ブチロラクトンから選ばれる少なくとも１種を含有する溶媒である、前記［７］項に記載の熱硬化性組成物。
［９］ カルボキシル基含有化合物（Ａ）以外のエポキシ硬化剤（Ｄ）をさらに含有する、前記［１］〜［８］の何れか一項に記載の熱硬化性組成物。
［１０］ エポキシ硬化剤（Ｄ）が、酸無水物系硬化剤、フェノール樹脂系硬化剤、アミンアダクト、ポリカルボン酸系硬化剤、ポリアミン系硬化剤および触媒型硬化剤から選ばれる少なくとも１種である、前記［９］項に記載の熱硬化性組成物。
［１１］ 前記［１］〜［１０］の何れか一項に記載の熱硬化性組成物からなるインクジェット用インク。
［１２］ 前記［１１］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、および該塗膜を硬化処理する工程を経て得られた硬化膜またはパターン状硬化膜。
［１３］ 前記［１１］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、および該塗膜を硬化処理する工程を有する、インクの塗布方法。
［１４］ 前記［１１］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、および該塗膜を硬化処理する工程を有する、硬化膜またはパターン状硬化膜の形成方法。
［１５］ フィルム基板と、該基板上に前記［１４］項に記載の形成方法により形成された硬化膜またはパターン状硬化膜とを有する硬化膜付き基板。
［１６］ シリコンウエハー基板と、該基板上に前記［１４］項に記載の形成方法により形成された硬化膜またはパターン状硬化膜とを有する硬化膜付き基板。
［１７］ 前記［１５］または前記［１６］項に記載の硬化膜付き基板を有する電子部品。 [1] (A) (i) Amic acid obtained by reacting amino compound (a1) represented by general formula (1) with acid anhydride (a2), and (ii) the amide acid or A thermosetting composition containing at least one carboxyl group-containing compound selected from ester compounds obtained by reacting the imidized product with an acid anhydride (a2 ′), and (B) an epoxy compound. .

[In Formula (1), Z is a divalent organic group. ]
[2] The thermal curing according to the above [1], wherein the acid anhydrides (a2) and (a2 ′) are each independently at least one selected from dicarboxylic acid anhydrides and tetracarboxylic dianhydrides. Sex composition.
[3]
The dicarboxylic acid anhydride is a compound represented by the general formula (2),
Tetracarboxylic dianhydride is a compound represented by the general formula (3),
The thermosetting composition according to item [2].

[In Formula (2), X is

Either
In formula (3), Y is

{Where R ¹ is a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ -

R ² is any one of a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —. It is. }. ]
[4] The carboxyl group-containing compound (A) is at least one selected from compounds represented by the general formulas (i-1) to (i-3) and (ii-1) to (ii-8). The thermosetting composition according to item [3].

[In formulas (i-1) to (i-3) and (ii-1) to (ii-8), X has the same meaning as X in formula (2), and Y represents Y in formula (3). Z is synonymous with Z in formula (1), and —CO—A—COOH is a residue of the compound represented by formula (2) or formula (3). ]
[5] Z in the general formula (1) is alkylene having 1 to 20 carbon atoms, a group in which any methylene in the alkylene is replaced with an aromatic group, or — (CH ₂ CH ₂ —O) _n —CH _{2. The} thermosetting composition according to any one of [1] to [4], which is a group represented by ₂ CH ₂ — (n is an integer of 1 to 10).
[6] The epoxy compound (B) is alkylene glycol diglycidyl ether, 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, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis ( N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and a group consisting of compounds represented by formulas (B1) to (B4) At least one compound That the [1] to thermosetting composition according to any one of [5].

[In formula (B1), p is an integer of 1-50. ]
[7] The thermosetting composition according to any one of [1] to [6], further including a solvent (C).
[8] The solvent (C) is ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene Glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene Glycol monoethyl ether, propylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 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-dimethylacetamide N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone. That the [7] The thermosetting composition according to item.
[9] The thermosetting composition according to any one of [1] to [8], further including an epoxy curing agent (D) other than the carboxyl group-containing compound (A).
[10] The epoxy curing agent (D) is at least one selected from acid anhydride curing agents, phenol resin curing agents, amine adducts, polycarboxylic acid curing agents, polyamine curing agents, and catalytic curing agents. The thermosetting composition as described in the item [9].
[11] An inkjet ink comprising the thermosetting composition according to any one of [1] to [10].
[12] A cured film or a patterned cured film obtained by applying the inkjet ink according to [11] above by an inkjet coating method to form a coating film, and curing the coating film .
[13] An ink coating method comprising a step of coating the inkjet ink according to the above [11] by an inkjet coating method to form a coating film, and a step of curing the coating film.
[14] Formation of a cured film or a patterned cured film, which includes a step of applying the inkjet ink according to the item [11] by an inkjet coating method to form a coating film, and a step of curing the coating film. Method.
[15] A substrate with a cured film, comprising a film substrate, and a cured film or a patterned cured film formed on the substrate by the formation method according to [14].
[16] A substrate with a cured film, comprising a silicon wafer substrate and a cured film or a patterned cured film formed on the substrate by the formation method according to [14].
[17] An electronic component having the substrate with a cured film according to the above [15] or [16].

According to the present invention, (1) a thermosetting composition capable of forming a cured film exhibiting good adhesion to a substrate, for example, for printed wiring board use or semiconductor use, (2) viscosity, boiling point of solvent Various parameters such as are optimized for ink jet printing, exhibiting good ink jet printability and excellent storage stability, (3) a relatively thick cured film (2 μm in one jetting) (4) Thermosetting that has good electrical characteristics, alkali resistance and thermal characteristics, and can form a cured film with a small amount of warping. A composition can be provided.
Therefore, according to the present invention, it is possible to improve the reliability and yield of electronic components.

  Hereinafter, each configuration of the present invention will be described.

[Thermosetting composition]
The thermosetting composition of the present invention contains a carboxyl group-containing compound (A) and an epoxy compound (B), and preferably further contains a solvent (C). The composition may contain an epoxy curing agent (D) other than the compound (A) and other additives.

<Carboxyl group-containing compound (A)>
Examples of the carboxyl group-containing compound (A) include at least one compound selected from the following amide acid (i) and the following carboxyl group-containing ester compound (ii).
(I) An amic acid obtained by reacting an amino compound (a1) represented by the general formula (1) described later and an acid anhydride (a2) (hereinafter also referred to as “amidic acid (i)”).
(Ii) an ester compound (hereinafter referred to as “carboxyl group”) obtained by reacting amic acid (i) or an imidized product thereof (hereinafter also referred to as “imidized product (i)”) with an acid anhydride (a2 ′). Also referred to as “containing ester compound (ii)” or “ester compound (ii)”.
Since compound (A) has carboxyl, it acts as an epoxy curing agent. That is, by the heat treatment, the carboxyl of the compound (A) and the epoxy of the epoxy compound (B) react with each other to cure and form a cured film. The cured film exhibits good adhesion to the substrate, has a small amount of warpage, and is excellent in electrical characteristics, alkali resistance characteristics, and thermal characteristics.
The acid anhydride (a2 ′) to be reacted with the amic acid (i) or its imidized product (i) may be the same as or different from the acid anhydride (a2) used in the synthesis of the amic acid (i). .
Hereinafter, reaction raw materials such as amino compound (a1), acid anhydride (a2) and acid anhydride (a2 ′), and a reaction solvent used in the synthesis of compound (A) will be described, and then synthesis of compound (A) will be described. The conditions will be described.

<Amino compound (a1)>
The amino compound (a1) is represented by the general formula (1).

式（１）中、Ｚは二価の有機基である。二価の有機基としては、炭素数１〜２０のアルキレン、前記アルキレン中の任意のメチレンをフェニレンなどの芳香族基に置き換えた基、ポリエチレングリコール〔―（ＣＨ₂ＣＨ₂―Ｏ）_n―ＣＨ₂ＣＨ₂―で表される基、ｎは１〜１０の整数である。〕などが挙げられる。炭素数１〜２０のアルキレンは、直鎖状であっても、分岐鎖状であってもよい。

In formula (1), Z is a divalent organic group. Examples of the divalent organic group include alkylene having 1 to 20 carbon atoms, a group in which any methylene in the alkylene is replaced with an aromatic group such as phenylene, polyethylene glycol [— (CH ₂ CH ₂ —O) _n —CH A group represented by ₂ CH ₂ —, n is an integer of 1 to 10; And the like. The alkylene having 1 to 20 carbon atoms may be linear or branched.

  Examples of the amino compound (a1) include 2-aminoethanol, 5-amino-1-pentanol, 2- (4-aminophenyl) ethanol, 2- (2-aminoethoxy) ethanol and the like. Among these, when the thermosetting composition of the present invention is used as an inkjet ink, the compatibility of the ink is excellent, and the adhesion of the cured film obtained from the ink to the metal is excellent. 2-Aminoethoxy) ethanol and 2- (4-aminophenyl) ethanol are preferred.

<Acid anhydride (a2)>
The acid anhydride (a2) is not particularly limited as long as it has an acid anhydride group. In the present invention, from the viewpoint of obtaining a thermosetting composition having a low viscosity and a high concentration of the carboxyl group-containing compound (A), the number of acid anhydride groups in the acid anhydride (a2) is one or two. It is preferable. That is, as the acid anhydride (a2), dicarboxylic acid anhydride and tetracarboxylic dianhydride are preferable.

-Compound having one acid anhydride group-
Examples of the compound having one acid anhydride group include dicarboxylic acid anhydrides.
Examples of the dicarboxylic acid anhydride include a compound represented by the general formula (2), tetrapropenyl succinic anhydride, tetradecenyl succinic anhydride, octadecenyl succinic anhydride, and 2-dodecen-1-yl succinic acid. Acid anhydride, 4-methylphthalic anhydride, 4-t-butylphthalic anhydride, 4-fluorophthalic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 1,3-cyclohexanedicarboxylic acid An acid anhydride, glutaric acid anhydride, etc. are mentioned.

式（２）中、Ｘは、

In the formula (2), X is

の何れかである。
ジカルボン酸無水物の中でも、カルボキシル基含有化合物（Ａ）の濃度が高い熱硬化性組成物（該組成物はインクジェット用インクとして好適に使用することができる。）を調製できる点で、一般式（２）で表される化合物、すなわちコハク酸無水物、マレイン酸無水物、シトラコン酸無水物、フタル酸無水物、ｃｉｓ−４−シクロヘキセン−１，２−ジカルボン酸無水物、トリメリット酸無水物およびｃｉｓ−１，２−シクロヘキサンジカルボン酸無水物が好ましく；マレイン酸無水物、シトラコン酸無水物、コハク酸無水物、フタル酸無水物、トリメリット酸無水物が特に好ましい。

Any of them.
Among dicarboxylic acid anhydrides, a general formula (in which a thermosetting composition having a high concentration of the carboxyl group-containing compound (A) (the composition can be suitably used as an inkjet ink) can be prepared. 2) compounds represented by succinic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride and Cis-1,2-cyclohexanedicarboxylic anhydride is preferred; maleic anhydride, citraconic anhydride, succinic anhydride, phthalic anhydride, and trimellitic anhydride are particularly preferred.

-Compound having two acid anhydride groups-
Examples of the compound having two acid anhydride groups include tetracarboxylic dianhydride.
Examples of the tetracarboxylic dianhydride include a compound represented by the general formula (3), 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfone tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 , 3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), methylcyclobutane tetracarboxylic dianhydride, Cyclopentanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride, ethylenediaminetetracarboxylic dianhydride, , 3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene succinic dianhydride and formulas a1-1 to a1-58 And the like.

式（３）中、Ｙは、

In formula (3), Y is

の何れかである｛ここで、Ｒ¹は、単結合、―Ｏ―、―ＣＯ―、―ＳＯ₂―、―ＣＨ₂―、―Ｃ（ＣＨ₃）₂―、―Ｃ（ＣＦ₃）₂―、

{Where R ¹ is a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ -

の何れかであり、Ｒ²は、単結合、―Ｏ―、―ＣＯ―、―ＳＯ₂―、―ＣＨ₂―、―Ｃ（ＣＨ₃）₂―、―Ｃ（ＣＦ₃）₂―の何れかである。｝。

R ² is any one of a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —. It is. }.

Among the tetracarboxylic dianhydrides, the compound represented by the general formula (3), butane tetracarboxylic dianhydride, particularly the compound represented by the general formula (3) is soluble in the solvent (C). Is preferable because a thermosetting composition having a high concentration of the compound (A) can be prepared (the composition can be suitably used as an inkjet ink).
Moreover, although high transparency is required depending on the use of the inkjet ink, in such a case, the compound represented by the general formula (3), butanetetracarboxylic dianhydride is preferable, and pyromellitic acid Dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ In particular diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropanoic dianhydride, cyclobutanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride preferable.
As the acid anhydride (a2), only one type may be used, or two or more types may be mixed and used.

<Acid anhydride (a2 ′)>
The acid anhydride (a2 ′) to be reacted with the amide acid (i) or its imidized product (i) is not particularly limited as long as it has an acid anhydride group, and the same as the acid anhydride (a2) described above. Can be used. That is, the compound represented by General formula (4) is mentioned.

式（４）中、Ａは式（２）中のＸと同義であるか、あるいは

In formula (4), A has the same meaning as X in formula (2), or

（式中、Ｙは式（３）中のＹと同義である。）で表される二価の基である。

(Wherein Y is the same as Y in formula (3)).

<Reaction solvent>
When synthesizing the carboxyl group-containing compound (A), a reaction solvent is usually used.
As a reaction solvent, ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, aniso , Ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether ( -Ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 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, γ-butyrolactone and the like.
Moreover, solvents other than the reaction solvent illustrated above can also be used by mixing with the reaction solvent.
Only 1 type may be used for a reaction solvent, and 2 or more types may be mixed and used for it.
By the way, when the reaction solvent remains when the synthesis of the carboxyl group-containing compound (A) is completed, the reaction solvent can be used as the solvent (C). Among the reaction solvents, the compatibility with the other components in the thermosetting composition is good, and since the composition has a low viscosity, when it is used as an ink for ink jet, it is easy to eject from the ink jet head. N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyrolactone are preferred.

  <Synthesis conditions of carboxyl group-containing compound (A)>

-Amic acid (i) or imidized product thereof (i)-
Amic acid (i) can be synthesized under mild reaction conditions by mixing amino compound (a1) and acid anhydride (a2). The mild reaction conditions are, for example, a normal pressure, a temperature of 5 to 60 ° C., a reaction time of 0.2 to 20 hours, preferably a temperature of 5 to 30 ° C. and a reaction time of 0.2 to 10 hours. The condition is that the acid anhydride group of the acid anhydride (a2) is allowed to react without activating the carboxyl formed by ring opening by the reaction. The activation of carboxyl is, for example, conversion to acid chloride.
Under the above mild reaction conditions, the carboxyl produced by the reaction of the amino of the amino compound (a1) and the acid anhydride group of the acid anhydride (a2) reacts with the amine of the amino compound (a1) or imidizes. Therefore, the amic acid (i) having a free carboxyl can be obtained.

  The imidization of the amic acid (i) can be performed by a thermal method or a chemical method using a dehydration catalyst and a dehydrating agent, but it is preferable to proceed by a thermal method that can be used without performing a purification treatment. The imidation is, for example, heating at normal pressure and a temperature of usually 50 to 200 ° C., preferably 60 to 180 ° C., a reaction time of usually 0.2 to 20 hours, preferably 0.5 to 10 hours, and without using a catalyst. The process can proceed. The amic acid (i) can be converted into an imide structure by the heating step.

Further, instead of the above mild reaction conditions, the synthesis of amic acid (i) and its imidization may be advanced by the heating step. That is, the imido compound (i) may be synthesized by mixing the amino compound (a1) and the acid anhydride (a2) and proceeding the reaction under the heating step.
The preparation amount of the amino compound (a1) is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, per 1 mol of the acid anhydride group of the acid anhydride (a2).

-Carboxyl group-containing ester compound (ii)-
Hydroxyl derived from the amino compound (a1) exists in the amic acid (i) or imidized product (i) thereof. Therefore, the amino acid (a1) -derived hydroxyl and the acid anhydride (a2 ′) acid can be obtained by reacting the amide acid (i) or its imidized product (i) with the acid anhydride (a2 ′). Reaction with an anhydride group produces carboxyl. In this way, an amide acid having an ester or an imidized product having an ester, that is, a carboxyl group-containing ester compound (ii) can be synthesized. The esterification can be carried out, for example, under normal pressure at a temperature of usually 50 to 200 ° C., preferably 60 to 180 ° C., a reaction time of usually 0.2 to 20 hours, preferably 0.5 to 10 hours.
The amic acid (i) or its imidized product (i) obtained as described above may be isolated by a purification treatment and then reacted with an acid anhydride (a2 ′), or a solution containing them. An acid anhydride (a2 ′) may be added to and reacted with the acid anhydride (a2 ′).

The amount of the acid anhydride (a2 ′) charged is usually 0.1 to 3 mol, preferably 0.5 to 2 mol, relative to 1 mol of hydroxyl of the amic acid (i) or imidized product (i) thereof. .
From the viewpoint of total charge, in the synthesis of the carboxyl group-containing compound (A), the number of moles of the amino compound (a1) is defined as _na1 , the total number of moles of the acid anhydrides (a2) and (a2 ′). When n _a2 is set, the molar ratio (n _a1 / n _a2 ) is usually set to 0.3 to 5.0, preferably 0.35 to 4.0, more preferably 0.40 to 3.0. Good. From the viewpoint of the compatibility of the carboxyl group-containing compound (A) in the thermosetting composition and the adhesion between the cured film formed from the thermosetting composition and the metal, the molar ratio is preferable.

The total amount of reaction solvent used is usually 100 parts by weight with respect to a total of 100 parts by weight of the amino compound (a1), the acid anhydride (a2) and the acid anhydride (a2 ′) from the viewpoint of smoothly proceeding the reaction. As mentioned above, Preferably it is 100-500 weight part.
The reaction solution or mixed solution obtained as described above contains the carboxyl group-containing compound (A) and the reaction solvent. The reaction solution or mixed solution containing the compound (A) may be used as it is, or the compound (A) may be isolated and used.
The carboxyl group-containing compound (A), including the epoxy compound (B), can be contained at a high concentration in the thermosetting composition of the present invention and the inkjet ink, and the composition and the ink have a low viscosity. is there. Therefore, the thermosetting composition and the inkjet ink of the present invention can form a relatively thick cured film (2 μm or more) by one jetting.

<Order of addition of reaction raw materials to reaction system>
The order of adding the reaction raw materials to the reaction system is not particularly limited.
In the synthesis of the amic acid (i), for example, a method in which the amino compound (a1) and the acid anhydride (a2) are simultaneously added to the reaction solvent, the acid anhydride (a2) is dissolved in the reaction solvent, and then the amino compound ( Any method such as a method of adding a1) or a method of adding an acid anhydride (a2) after dissolving the amino compound (a1) in a reaction solvent can be used.
In the synthesis of the carboxyl group-containing ester compound (ii), for example, the amino compound (a1) and the acid anhydride (a2) are mixed and reacted as described above, and then the obtained amide acid (i) or The imidized product (i) is isolated and mixed with the acid anhydride (a2 ′) and the reaction solvent, and the amino compound (a1) and the acid anhydride (a2) are mixed as described above. Any method can be used such as a method of adding an acid anhydride (a2 ′) after the reaction. Further, the amino compound (a1), the acid anhydride (a2) (a part of which corresponds to the acid anhydride (a2 ′)) and the reaction solvent are mixed to obtain the amic acid (i) and the ester compound. The synthesis of (ii) may proceed simultaneously.

<Specific examples of amic acid (i) and carboxyl group-containing ester compound (ii)>
Specific examples of amic acid (i) include compounds represented by general formulas (i-1) to (i-3), but are not limited thereto.

カルボキシル基含有エステル化合物（ii）の具体例としては、一般式（ii−１）〜（ii−８）で表される化合物が挙げられるが、これらに限定されるものではない。

Specific examples of the carboxyl group-containing ester compound (ii) include compounds represented by general formulas (ii-1) to (ii-8), but are not limited thereto.

  In formulas (i-1) to (i-3) and (ii-1) to (ii-8), X has the same meaning as X in formula (2), and Y is the same as Y in formula (3). Z is synonymous with Z in formula (1), -CO-A-COOH is the residue of the compound represented by formula (2) or formula (3), that is, A is in formula (2) Or a divalent group represented by the following formula (wherein Y has the same meaning as Y in formula (3)).

The concentration of the carboxyl group-containing compound (A) in the thermosetting composition of the present invention is preferably 1 to 80% by weight, and more preferably 5 to 60% by weight. When the concentration range is within this range, for example, when the thermosetting composition of the present invention is used for ink jet printing, a thick cured film can be formed while keeping the viscosity of the ink within an appropriate range.
When the reaction solution or mixed solution obtained at the synthesis of the compound (A) is mixed with other components as it is, the amount of the reaction solution or mixed solution used is preferably 15 to 70% by weight, More preferred is ˜60% by weight.
In addition, the density | concentration of a compound (A) is a density | concentration with respect to the whole composition.

<Epoxy compound (B)>
The epoxy compound (B) is not particularly limited as long as it is a compound having oxirane or oxetane, but a compound having two or more oxiranes is preferable.
Examples of the epoxy compound (B) include alkylene glycol diglycidyl ether, glycidyl ester type epoxy resin, 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, alicyclic epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, formulas (B1) to ( Table in B4) Compound, a polymer of a monomer having oxirane, copolymers of monomers with other monomers having an oxirane and the like.

式（Ｂ１）中、ｐは１〜５０の整数である。

In formula (B1), p is an integer of 1-50.

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

  Other monomers that copolymerize with oxirane-containing monomers include (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, chloromethylstyrene, (3-Ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide and the like.

  Preferred examples of the polymer of the monomer having oxirane and the copolymer of the monomer having oxirane and another monomer include polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, and benzyl methacrylate-glycidyl methacrylate copolymer. , 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, etc. Is mentioned. Use of these epoxy compounds is preferable because the heat resistance of the cured film formed from the ink jet ink comprising the thermosetting composition of the present invention is improved.

Among epoxy compounds (B), alkylene glycol diglycidyl ether, 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, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane and compounds represented by formulas (B1) to (B4) are preferred.
Commercially available products of the epoxy compound (B) include trade names "Epicoat 807", "Epicoat 815", "Epicoat 825", "Epicoat 827", "Epicoat 828", "Epicoat 828EL", "Epicoat 190P", "191P" (manufactured by Yuka Shell Epoxy Co., Ltd.), trade names "Epicoat 1001", "Epicoat 1004", "Epicoat 1256" (above, Japan Epoxy Resin Co., Ltd.), trade names "Araldite CY177", Trade name “Araldite CY184” (manufactured by Ciba Geigy Japan), trade names “Celoxide 2021P”, “Celoxide 3000”, “EHPE-3150” (Daicel Chemical Industries), trade name “Techmore VG3101L” (Mitsui) Chemical Co., Ltd.). Among these, the product name “Araldite CY184”, the product name “Celoxide 2021P”, the product name “Techmore VG3101L”, the product name “Epicoat 828”, and the product name “Epicoat 828EL” have particularly good flatness of the resulting cured film. Therefore, it is preferable.
As for an epoxy compound (B), only 1 type may be used and 2 or more types may be mixed and used for it.
Although the density | concentration of the epoxy compound (B) in the thermosetting composition of this invention is not specifically limited, 1 to 80 weight% is preferable and 10 to 60 weight% is further more preferable. Within this concentration range, the cured film formed from the curable composition of the present invention has good heat resistance, chemical resistance and flatness.
In addition, the density | concentration of an epoxy compound (B) is a density | concentration with respect to the whole composition.

<Solvent (C)>
The thermosetting composition of the present invention preferably further contains a solvent (C). The solvent (C) is not particularly limited as long as it can dissolve the compound (A) and the epoxy compound (B). In addition, even if the solvent alone does not dissolve the compound (A) or the epoxy compound (B), when the compound (A) or the epoxy compound (B) is dissolved by mixing with another solvent, It is also possible to use such a mixed solvent as the solvent (C).
The boiling point of the solvent (C) is usually 150 to 300 ° C, preferably 150 to 250 ° C.
As the solvent (C), ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Mechi Ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butyl ether) Xyl-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene Glycol monovinyl ether, methyl benzoate, ethyl benzoate, 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-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1 3-dimethyl-2-imidazolidinone, etc. γ- butyrolactone.

Among the solvents (C), the compatibility with other components in the thermosetting composition is good, and since the composition has a low viscosity, the ink jetting property is good when used as an inkjet ink. In this respect, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, cyclohexanone, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, and γ-butyrolactone are preferable.
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 such a ratio that the solid content concentration in the thermosetting composition of the present invention is 30 to 80% by weight, particularly 30 to 75% by weight. In addition, solid content means all components other than the solvent (C) in a thermosetting composition. When the reaction solution or mixed solution obtained at the time of synthesizing compound (A) is mixed with other components as it is, the solvent (C) includes the reaction solvent used at the time of synthesizing compound (A).

<Epoxy curing agent (D)>
In order to further improve the plating resistance and solder heat resistance of the resulting cured film, the thermosetting composition of the present invention may further contain an epoxy curing agent (D) other than the compound (A). Examples of the epoxy curing agent (D) include an acid anhydride curing agent, a phenol resin curing agent, an amine adduct, a polycarboxylic acid curing agent, a polyamine curing agent, and a catalyst curing agent.
When the epoxy curing agent (D) is used, the epoxy curing agent (D) is usually more than 0 parts by weight and 50 parts by weight or less with respect to 100 parts by weight of the carboxyl group-containing compound (A) in the thermosetting composition. , Preferably more than 0 parts by weight and 40 parts by weight or less, more preferably more than 0 parts by weight and 30 parts by weight or less.

  Acid anhydride curing agents include maleic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride , Hexahydrotrimellitic anhydride, styrene-maleic anhydride copolymer, and the like.

  Examples of the phenol resin-based curing agent include novolak-type phenol resins such as phenol novolak resins and cresol novolak resins; Bisphenol type resins such as A and bisphenol F; phenolic resins such as biphenyl type phenolic resins, resol type phenolic resins, phenol aralkyl resins, biphenyl skeleton-containing aralkyl type phenolic resins, triphenolalkane type resins and polymers thereof; naphthalene ring-containing phenols Examples thereof include resins, dicyclopentadiene-modified phenol resins, alicyclic phenol resins, and heterocyclic phenol resins.

Examples of the amine adduct include, but are not limited to, a reaction product of an amine and an epoxy, and three reaction products of a diamine, an acid anhydride, and an epoxy.
Specific examples of reactive organisms of amines and epoxies include reaction products of S510 (manufactured by Chisso) and 4-benzylpiperidine, and S510 (manufactured by Chisso) and 3,5-dimethylpiperidine. Reaction product, reaction product of Epicoat 828EL (Oilized Shell Epoxy Co., Ltd.) and 3,5-dimethylpiperidine, reaction product of Epicoat 828EL (Oilized Shell Epoxy Co., Ltd.) and 4-hydropiperidine Things.

Specific examples of the three reaction products of diamine, acid anhydride, and epoxy include a reaction product of 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of maleic anhydride. , S510 (manufactured by Chisso Corp.), 2 mol of reaction product, 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 3- (triethoxysilyl) propyl succinic anhydride 1 Reaction product of 1 mol of reactant and 2 mol of S510 (manufactured by Chisso), 1 mol of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1 mol of maleic anhydride And a reaction product of 2 moles of N-glycidyl phthalimide, 1 mole of Polea SL-100A (Ihara Chemical Industry Co., Ltd.) and 1 mole of maleic anhydride, Such as 10 (manufactured by Chisso Corporation) the reaction product of two moles and the like.
Examples of the polycarboxylic acid curing agent include a reaction product of 1 mol of oxydiphthalic anhydride and 2 mol of isoleucine, a reaction product of 1 mol of oxydiphthalic anhydride and 2 mol of leucine, and 1 mol of biphenyltetracarboxylic anhydride. A reaction product of 2 moles of leucine, a reaction product of 1 mole of biphenyltetracarboxylic anhydride and 2 moles of isoleucine, and the like can be mentioned.

<Other additives>
The thermosetting composition of the present invention may further contain other additives depending on the intended properties. Other additives include polymer compounds, alkenyl-substituted nadiimide compounds, silicon amic acid compounds, acrylic resins, polymerizable monomers, surfactants, antistatic agents, coupling agents, pH adjusters, rust inhibitors, preservatives , Antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, water-soluble polymers, pigments, dyes and the like.

<Polymer compound>
Examples of the polymer compound include polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol and polyoxyethylene, and polyimide such as polyamic acid and soluble polyimide. A polymer compound is preferable.
As the polymer compound, a polyamic acid obtained by using at least tetracarboxylic dianhydride and diamine and having a structural unit represented by the following formula or an imidized polymer thereof is particularly preferable.

式中、Ｘは炭素数２〜１００の四価の有機基であり、Ｙは炭素数２〜１００の二価の有機基である。

In the formula, X is a tetravalent organic group having 2 to 100 carbon atoms, and Y is a divalent organic group having 2 to 100 carbon atoms.

  Examples of the tetracarboxylic dianhydride include compounds exemplified as examples of the tetracarboxylic dianhydride of the acid anhydride (a2). Examples of the diamine include compounds represented by the following formula.

式中、Ｙは炭素数２〜１００の二価の有機基である。
ジアミンとしては、例えば、ｍ−キシリレンジアミン、ｐ−キシリレンジアミンおよび下記式（Ｉ）〜（VII）で表される化合物が挙げられる。

In the formula, Y is a divalent organic group having 2 to 100 carbon atoms.
Examples of the diamine include m-xylylenediamine, p-xylylenediamine, and compounds represented by the following formulas (I) to (VII).

In formula (I), A ¹ is — (CH ₂ ) _m —, where m is an integer of 2-6.
In the formulas (III), (V) and (VII), A ² represents a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO. _{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - (CH 2) n -, - O- (CH 2) n -O- or -S- (CH _{2) n} -S -Where n is an integer from 1-6.
In formulas (VI) and (VII), two A ³ groups are each independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF _{3). 2} ) or alkylene having 1 to 3 carbon atoms.
In the above formulas (I) to (VII), at least one hydrogen 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 following formulas (I-1) to (I-3).

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

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

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

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

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

  Examples of the compound represented by the formula (VII) include compounds represented by the following 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, 1,1-bis [4- (4-aminobenzyl) phenyl] methane and the like can be preferably used.
Examples of the diamine further include a compound represented by the following formula (VIII).

式（VIII）中、Ａ⁴は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−または−（ＣＨ₂）_p−であり、ここでｐは１〜６の整数である。Ｒ⁶は、ステロイド骨格を有する基、または、シクロヘキサン環およびベンゼン環からなる群より選ばれる少なくとも１種の環構造を有する基である。なお、ベンゼン環に結合している２つのアミノ基の位置関係がパラ位のときは、Ｒ⁶は炭素数１〜３０のアルキルであってもよく、前記位置関係がメタ位のときは、Ｒ⁶は炭素数１〜１０のアルキル、または−Ｆ、−ＣＨ₃、−ＯＣＨ₃、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂もしくは−ＯＣＦ₃で置き換えられていてもよいフェニルであってもよい。
Ｒ⁶における上記炭素数１〜３０のアルキルおよび炭素数１〜１０のアルキルは、直鎖状であっても分岐状であってもよい。これらのアルキルにおいては、任意の−ＣＨ₂−が−ＣＦ₂−、−ＣＨＦ−、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、任意の−ＣＨ₃が−ＣＨ₂Ｆ、−ＣＨＦ₂または−ＣＦ₃で置き換えられていてもよい。
式（VIII）において、２つのアミノ基はフェニル環炭素に結合しているが、２つのアミノ基の結合位置関係は、メタ位またはパラ位であることが好ましい。さらに２つのアミノ基はそれぞれ、「Ｒ⁶−Ａ⁴−」のベンゼン環への結合位置を１位としたときに、３位および５位、または２位および５位に結合していることが好ましい。

In the formula (VIII), A ⁴ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _p —, where p is 1 to 6 Is an integer. R ⁶ is a group having a steroid skeleton or a group having at least one ring structure selected from the group consisting of a cyclohexane ring and a benzene ring. When the positional relationship between the two amino groups bonded to the benzene ring is para, R ⁶ may be alkyl having 1 to 30 carbon atoms, and when the positional relationship is meta, R 6 ⁶ alkyl having 1 to 10 carbon atoms, or _{-F,, -CH 3, -OCH 3} , -OCH 2 F, or may be phenyl optionally replaced by -OCHF ₂ or -OCF _3.
The alkyl having 1 to 30 carbon atoms and the alkyl having 1 to 10 carbon atoms in R ⁶ may be linear or branched. In these alkyls, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, and any —CH _{3 —} May be replaced by —CH ₂ F, —CHF ₂ or —CF ₃ .
In formula (VIII), the two amino groups are bonded to the phenyl ring carbon, but the bonding position relationship between the two amino groups is preferably the meta position or the para position. Further, the two amino groups may be bonded to the 3-position and 5-position, or the 2-position and 5-position, respectively, when the bonding position of “R ⁶ -A ⁴ —” to the benzene ring is 1-position. preferable.

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

In the formulas (VIII-1), (VIII-2), (VIII-7) and (VIII-8), R ⁷ is an organic group having 1 to 30 carbon atoms, alkyl having 3 to 12 carbons or carbon number It is preferably 3 to 12 alkoxy, more preferably alkyl having 5 to 12 carbons or alkoxy having 5 to 12 carbons.
In formulas (VIII-3) to (VIII-6) and (VIII-9) to (VIII-11), R ⁸ is an organic group having 1 to 30 carbon atoms, alkyl having 1 to 10 carbon atoms or carbon number It is preferably 1 to 10 alkoxy, more preferably alkyl having 3 to 10 carbons or alkoxy having 3 to 10 carbons.

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

In formulas (VIII-12) to (VIII-15), R ⁹ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 4 to 16 carbon atoms, and alkyl having 6 to 16 carbon atoms. More preferably.
In Formula (VIII-16) and Formula (VIII-17), R ¹⁰ is an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, and an alkyl group having 8 to 20 carbon atoms. More preferably it is.

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

Formulas (VIII-18), (VIII-19), (VIII-22), (VIII-24), (VIII-25), (VIII-28), (VIII-30), (VIII-31), ( In (VIII-36) and (VIII-37), R ¹¹ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons, and having 3 carbon atoms. More preferably, it is -12 alkyl or C3-C12 alkoxy.
Formulas (VIII-20), (VIII-21), (VIII-23), (VIII-26), (VIII-27), (VIII-29), (VIII-32) to (VIII-35) and ( VIII-38) in, R ¹² is hydrogen, -F, alkyl having 1 to 12 carbon atoms, having 1 to 12 carbon atoms alkoxy, -CN, -OCH ₂ F, a -OCHF ₂ or -OCF _3, carbon atoms It is preferably 3 to 12 alkyl or C 3 to C 12 alkoxy.
In formulas (VIII-33) and (VIII-34), A ⁵ is alkylene having 1 to 12 carbons.

Examples of the compound represented by the formula (VIII) further include compounds represented by the following formulas (VIII-39) to (VIII-48).

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

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

In formulas (IX) and (X), R ¹³ is hydrogen or —CH ₃ , and two R ^{14 s} are each independently hydrogen, alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons, Two A ⁶ groups are each independently a single bond, —C (═O) — or —CH ₂ —.
In the formula (X), R ¹⁵ and R ¹⁶ are each independently hydrogen, alkyl having 1 to 20 carbons or phenyl.
In formula (IX), “NH ₂ —Ph—A ⁶ —O—” (—Ph— represents phenylene) bonded to the B ring of the steroid nucleus is bonded to the 6-position carbon of the steroid nucleus. It is preferable. Further, the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to the bonding position of A ^{6 to} the phenyl ring.
In formula (X), two “NH ₂ — (R ¹⁶ —) Ph—A ⁶ —O—” (—Ph— represents phenylene) are each bonded to a phenyl ring carbon. the steroid nucleus and the ring when ^{_{"NH 2 - - (R 16)}} Ph-a 6 -O- " is considered to be bonded, the steroid nucleus and ^{_{"NH 2 - (R 16 -)}} Ph-a 6 -O The positional relationship with “−” is preferably the meta position or the para position. The two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to A ⁶ .

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

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

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

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

In the formula (XII), R ¹⁸ is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable. R ¹⁹ is hydrogen or alkyl having 1 to 30 carbons, and among these, alkyl having 1 to 10 carbons is preferable. Two A ^{9 s} are each independently —O— or alkylene having 1 to 6 carbons.
In formula (XI), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta 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 ²⁰ is hydrogen or alkyl having 1 to 20 carbons.
In formulas (XI-4) to (XI-9), R ²¹ is hydrogen or alkyl having 1 to 20 carbons, and preferably hydrogen or alkyl having 1 to 10 carbons.

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

In formulas (XII-1) to (XII-3), R ²² is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable, and R ²³ is hydrogen or having 1 to 30 carbons. Among these, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.
Further, examples of diamines include diethylene glycol bis (3-aminopropyl) ether, 1,2-bis (2-aminoethoxy) ethane, 1,4-butanediol bis (3-aminopropyl) ether, 3,9-bis. (3-Aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-bis (4-aminophenoxy) biphenyl, 1,6-bis (4-((4 -Aminophenyl) methyl) phenyl) hexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,4- Bis (3-aminopropyl) piperazine, N, N′-bis (3-aminopropyl) ethylenediamine, 1,4-bis (aminomethyl) cyclohexane, 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 primary 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, or a siloxane-based diamine having a siloxane bond alone or mixed with a compound mentioned as a compound having two other primary amino groups Can be used.

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

In the formula (XIII), R ³ and R ⁴ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁵ is methylene or phenylene optionally substituted with alkyl, and two x's are independently 1 is an integer of 1 to 6, and y is an integer of 1 to 70. A plurality of R ³ , R ⁴ and R ⁵ may be the same or different from each other. Moreover, although high transparency is required depending on a use, it is especially preferable to use the compound which is an integer of y = 1-15 in such a case.

More preferably, examples of the diamine include compounds represented by the following formulas (11) to (18). In the following formulae, R ²⁴ and R ²⁵ are each independently alkyl having 3 to 20 carbon atoms.

  In the present invention, examples of the diamine further include compounds represented by the formulas (XV-15) and (XV-16).

  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), m and n are positive integers, and the molecular weight is 1200 to 1300. As a specific product, there is POLA SL-100A manufactured by Ihara Chemical Co., Ltd.

  In the present invention, the polymer compound refers to a compound having a structural unit. 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 composition. 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 (C) of a high molecular compound is especially high as a weight average molecular weight is 2,000 or less, the density | concentration of the high molecular compound in a thermosetting composition can be made high. For this reason, the softness | flexibility and heat resistance of the cured film obtained by apply | coating a thermosetting composition can be improved.

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

<Alkenyl-substituted nadiimide compound>
The alkenyl-substituted nadiimide compound is not particularly limited as long as it has at least one alkenyl-substituted nadiimide structure in the molecule. Preferably, for example, a compound represented by the formula (II-) described in International Publication No. 2008/059986 pamphlet is used. Examples thereof include alkenyl-substituted nadiimide compounds represented by 1).

In formula (II-1), R ¹⁴ and R ¹⁵ are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 12 carbons. Aryl or benzyl, n is an integer from 1 to 2,
When n = 1, R ¹⁶ is hydrogen, alkyl having 1 to 12 carbons, hydroxyalkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,-{( C _q H _2q ) O _t (C _r H _2r O) _u C _s H _2s X} (where q, r and s are each independently an integer of 2 to 6, t is an integer of 0 or 1, u is A polyoxyalkylene alkyl represented by an integer of 1 to 30, X is hydrogen or a hydroxyl group,-(R) _a -C ₆ H ₄ -R ¹⁷ (where a is an integer of 0 or 1, R is A group represented by alkylene having 1 to 4 carbon atoms, R ¹⁷ represents hydrogen or alkyl having 1 to 4 carbon atoms, and —C ₆ H ₄ —TC ₆ H ₅ (where T is —CH ₂ -, -C (CH ₃ ) _2- , -CO-, -S- or SO _2- ), or an aromatic ring of these groups. 1 to 3 hydrogens are replaced by hydroxyl groups,
When n = 2, R ¹⁶ is alkylene represented by —C _p H _2p — (wherein p is an integer of 2 to 20), cycloalkylene having 5 to 8 carbon atoms, — {(C _q H _{2q O) t (C r H} 2r O) u C s H 2s} - ( wherein, q, r, s are each independently an integer of 2 to 6, t is an integer of 0 or 1, u is from 1 to 30 polyoxyalkylene represented by the integer which is), arylene having 6 to 12 carbon _{^{atoms, - (R 17) a -C}} 6 H 4 -R 18 - ( wherein, a is an integer of 0 or 1, R ¹⁷ And R ¹⁸ are each independently a group having 1 to 4 carbon atoms, —C ₆ H ₄ —TC ₆ H ₄ — (wherein T is —CH ₂ —, —C ( CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O—, —S—, —SO ₂ —), or On the aromatic ring of these groups 1-3 hydrogen formation is a group which is replaced by a hydroxyl group.
Among the alkenyl-substituted nadiimide compounds represented by the formula (II-1),
R ¹⁴ and R ¹⁵ are each independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons or benzyl,
n is 2,
Alkylene in which R ¹⁶ is represented by —C _p H _2p — (wherein p is an integer of 2 to 10), — (R ¹⁷ ) _a —C ₆ H ₄ —R ¹⁸ — (where a Is an integer of 0 or 1, R ¹⁷ and R ¹⁸ are each independently alkylene having 1 to 4 carbon atoms, or —C ₆ H ₄ —TC ₆ H ₄ — (wherein T represents —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O—, —S— or —SO ₂ —. Is a group represented by
Alkenyl substituted nadiimide compounds are preferred.
Among the alkenyl-substituted nadiimide compounds represented by the formula (II-1), R ¹⁴ and R ¹⁵ are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, and R ¹⁶ is — (CH _{2) 6} -, a group represented by the group or the following formula represented by the following formula (II-2) (II- 3), an alkenyl-substituted nadiimide compounds are particularly preferred.

  The alkenyl-substituted nadiimide compound concentration in the thermosetting composition of the present invention is usually 0 to 40% by weight, preferably 0 to 20% by weight. In such a concentration range, good characteristics as an insulating film may be imparted.

<Silicon amic acid compound>
The silicon amide acid compound is not particularly limited as long as it is a silicon amide acid compound having an amide acid structure in the molecule. For example, at least two amide acids in the molecule described in WO 2008/123190 Pamphlet are used. Examples thereof include a silicon amide acid represented by the following formula (III) or a silicon amide acid represented by the following formula (IV).
Among the silicon amide acids represented by the formula (III), silicon amide acids represented by the following formula (III-1), (III-2) or (III-3) are preferable. Among the silicon amide acids represented by the formula (IV), silicon amide acids represented by the following formulas (IV-1), (IV-2), (IV-3) or (IV-4) are preferable.

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

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

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

In formulas (IV-1), (IV-2), (IV-3) and (IV-4), R ¹ , R ² and R ³ are each independently hydrogen, halogen or monovalent from 1 to 100 carbon atoms. And at least one of R ¹ , R ² and R ³ contains an alkoxy group having 1 to 20 carbon atoms, and a is an integer of 1 to 20. R in the formula (IV-3) is a monovalent organic group having 2 to 30 carbon atoms. R in the formula (IV-4) is hydrogen or alkyl having 1 to 20 carbons.
The silicon amic acid compound concentration in the thermosetting composition of the present invention is usually 0 to 30% by weight, preferably 0 to 20% by weight. When the concentration is within such a range, good characteristics as an insulating film may be imparted.

<Acrylic resin>
An acrylic resin will not be specifically limited if it is resin which has an acrylic group or a methacryl 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 ( Mention may be made of (meth) acrylates. 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, p-vinylphenyl- 3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) ) Acryloxymethyl oxetane, (meth) acrylic acid, Chill (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, (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, poly Restyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloylmorpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, (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] And mono [2- (meth) acryloyloxyethyl maleate] and mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate.

  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, 1,4-cyclohexanedimethanol diacrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol diacrylate, trimethylolpropane diacrylate, dipentaerythritol diacrylate Mention may be made of the over door.

  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, Mention may be made of ethylene oxide-modified phosphoric acid tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, urethane (meth) acrylate.

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

<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 trifunctional or higher polyfunctional (meth) acrylate. As the polymerizable monomer, only one kind may be used, or two or more kinds 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 ( Mention may be made of (meth) acrylates.

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, p-vinylphenyl- 3-ethyloxeta-3-ylmethyl ether, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane, 4-trifluoromethyl-2- (meth) ) Acryloxymethyl oxetane, (meth) acrylic acid, Chill (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) Acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, vinyltoluene, (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 , Polystyrene macromonomer, polymethyl methacrylate macromonomer, N-acryloylmorpholine, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, (meth) acrylate of ethylene oxide adduct of lauryl alcohol, (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] And mono [2- (meth) acryloyloxyethyl maleate] and mono [2- (meth) acryloyloxyethyl] cyclohexene-3,4-dicarboxylate.

  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 Mention may be made of acrylate and 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, Mention may be made of ethylene oxide-modified phosphoric acid tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate and urethane (meth) acrylate.

  Although the polymerizable monomer density | concentration in the thermosetting composition of this invention is not specifically limited, 0.1 to 50 weight% is preferable and 1 to 40 weight% is further more preferable. Within such a concentration range, the cured film formed from the thermosetting composition of the present invention has good heat resistance.

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

As the surfactant, for example, trade names “Byk-300”, “Byk-306”, “Byk-335”, and “Byk-310” can be applied to the thermosetting composition of the present invention. Silicone surfactants such as “Byk-341”, “Byk-344”, “Byk-370” (manufactured by Big Chemie); trade names “Byk-354”, “ByK-358”, “ Acrylic surfactants such as “Byk-361” (by Big Chemie); fluorines such as “DFX-18”, “Factent 250”, “Factent 251” (manufactured by Neos) There may be mentioned system surfactants.
Only one type of surfactant may be used, or a mixture of two or more types may be used.

<Antistatic agent>
The antistatic agent can be used for preventing charging of the thermosetting composition of the present invention, and is used in an amount of 0.01 to 1% by weight in 100% by weight of the thermosetting composition of the present invention. It is preferred that
The antistatic agent is not particularly limited, and a known antistatic agent can be used. Specific examples thereof include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, and 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.

<Coupling agent>
The coupling agent is not particularly limited, and a known coupling agent can be used, and it is used in an amount of 0.01 to 3% by weight in 100% by weight of the thermosetting composition of the present invention. Is preferred. A silane coupling agent is preferable as the coupling agent. Specific examples of the silane coupling agent include trialkoxysilane compounds and dialkoxysilane compounds. Only 1 type may be used for a coupling agent, and 2 or more types may be mixed and used for it.

  Examples of trialkoxysilane compounds or dialkoxysilane compounds include γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, and γ-acryloylpropylmethyldisilane. Ethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-aminopropylmethyldimethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyltrimethoxysilane, N-aminoethyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxy Silane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-amino Propyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane . Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane are particularly preferable.

<Method for preparing thermosetting composition>
The thermosetting composition of the present invention uniformly contains a carboxyl group-containing compound (A), an epoxy compound (B), and a solvent (C), an epoxy curing agent (D), and other additives as necessary. It can be prepared by mixing.
Further, the thermosetting composition of the present invention is prepared by using the reaction solution or mixed solution obtained at the time of synthesizing the carboxyl group-containing compound (A) as it is, the epoxy compound (B), and the solvent (C), epoxy as necessary. It can also be prepared by uniformly mixing with the curing agent (D), other additives and the like. The reaction solution or mixed solution contains at least one carboxyl group-containing compound (A) selected from amido acid (i) and carboxyl group-containing ester compound (ii), imidized product (i), reaction solvent, and the like. Is included.
The thermosetting composition of the present invention can optimize various parameters such as viscosity, surface tension, and boiling point of the solvent for ink jet printing, exhibits good ink jet printability (for example, drawability), and is stable in storage. Excellent in properties.

[Ink-jet ink]
The ink-jet ink of the present invention comprises the above-mentioned thermosetting composition.

<Inkjet ink viscosity>
The viscosity of the inkjet ink of the present invention at the temperature (ejection temperature) when ejected from the inkjet head is usually 1 to 50 mPa · s, preferably 5 to 20 mPa · s, more preferably 8 to 15 mPa · s. When the viscosity is in the above range, jetting accuracy by the ink jet coating method is improved. If the viscosity is less than 15 mPa · s, ink jet ejection defects do not occur.
Since jetting is often performed at room temperature (25 ° C.), the viscosity of the inkjet ink of the present invention at 25 ° C. is usually 1 to 50 mPa · s, preferably 5 to 20 mPa · s, more preferably 8 to 15 mPa · s. s. If the viscosity at 25 ° C. is less than 15 mPa · s, ink jet ejection defects do not occur.

<Surface tension of inkjet ink>
The surface tension of the inkjet ink of the present invention at 25 ° C. is usually 20 to 70 mN / m, preferably 20 to 40 mN / m. When the surface tension is in the above range, good droplets can be formed by jetting and a meniscus can be formed.

[Curing film or patterned cured film]
The cured film or patterned cured film of the present invention is obtained through a step of applying the inkjet ink of the present invention by, for example, an inkjet coating method to form a coating film, and a step of curing the coating film. Heat treatment such as a hot plate or an oven can be used for forming the cured film. In addition, the formation of the cured film is not limited to heat treatment, and treatment such as UV treatment, ion beam, electron beam, and gamma ray can also be used.
When ink is printed in a pattern using an ink jet coating method, a patterned cured film (patterned cured film) is formed. In the present specification, unless otherwise stated, hereinafter, the cured film includes a patterned cured film.
The insulating film made of the cured film of the present invention, for example, for printed wiring board use or semiconductor use, exhibits good adhesion with a substrate, has high heat resistance and high electrical insulation, has sufficient mechanical strength, The amount of warpage is small, and the reliability and yield of electronic components can be improved.

[Inkjet ink application method]
The ink jet ink coating method of the present invention includes a step of coating the above ink jet ink by the ink jet coating method to form a coating film, and a step of curing the coating film.
The ink of the present invention can be ejected by various methods by appropriately selecting the contained components. According to the inkjet coating method, the inkjet ink of the present invention is applied in a predetermined pattern. Can do.

When the ink of the present invention is applied by an ink jet application method, there are various types depending on the ink discharge 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.
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 may be configured such that they are integrated so as not to be separated. The ink container is integrated with the coating head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the apparatus via an ink supply member such as a tube. It may be in the form of supplying ink to the coating 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.

[Method of forming cured film]
The method for forming a cured film of the present invention includes a step of applying the above-described inkjet ink by an inkjet coating method to form a coating film, and a step of curing the coating film.
After forming the above-mentioned coating film, the solvent is usually removed by vaporization or the like by heating with a hot plate or oven, that is, drying. The drying conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 120 ° C., and 5 to 15 minutes when using an oven, and 1 to 5 minutes when using a hot plate. By such drying, a coating film having a shape capable of holding the shape on the substrate is formed.
In addition, when the viscosity of the inkjet ink of the present invention is high, the inkjet head is heated (preferably 40 to 120 ° C.) to heat the ink, and the viscosity of the ink is lowered before coating.

Inkjet coating method ejects (draws) ink only on the necessary parts, so the amount of material used is much smaller than that of photolithography, which was used to form a conventional insulating film (polyimide film). Since it is not necessary to use a mask, a large variety of insulating films can be mass-produced, and the number of processes required for manufacturing is small.
After forming the coating film, in order to cure the epoxy compound (B), a curing treatment is usually performed at 150 to 350 ° C, preferably 150 to 300 ° C. At this time, when an oven is used, a final cured film can be obtained by performing a curing treatment usually for 30 to 120 minutes, and when a hot plate is used, usually 5 to 30 minutes. Note that the curing treatment is not limited to heat treatment, and treatment such as UV treatment, ion beam, electron beam, or gamma ray irradiation may be performed.

The thermosetting composition according to a preferred embodiment of the present invention has a high solid content concentration and a high concentration of the carboxyl group-containing compound (A). For this reason, the cured film obtained as described above is thicker than a cured film formed by applying and curing a conventional polyimide ink jet ink, and its thickness is usually 2 μm or more, preferably 2 to 2 μm. 10 μm.
Thus, a thick cured film can be obtained from the thermosetting composition according to a preferred embodiment of the present invention by one jetting. For this reason, when forming a thick insulating film of about 10 μm, for example, the number of overcoats can be reduced as compared with the conventional inkjet ink, and the manufacturing process of the insulating film can be shortened.

  When forming a pattern film using the ink-jet ink of the present invention, it is only necessary to draw on a necessary portion by ink-jet printing. For this reason, the amount of material used is overwhelmingly small compared with other methods such as etching, and it is not necessary to use a photomask, so that it is possible to mass-produce a large variety of products and reduce the number of steps required for manufacturing. .

[Substrate with cured film]
The substrate with a cured film of the present invention has a film substrate or a silicon wafer substrate, and a cured film or a patterned cured film formed on the substrate by the above-described method for forming a cured film. For example, the ink of the present invention is applied to the entire surface or a predetermined pattern (line shape or the like) by an inkjet application method on a substrate such as a polyimide film or a silicon wafer substrate on which wiring is formed, and then as described above. The substrate is dried and further heated to form a cured film.

The cured film of the present invention is preferably formed on the above-described film substrate or silicon wafer substrate, but the type of the substrate is not particularly limited to these and can be formed on a known substrate.
As a substrate applicable to the present invention, for example, a glass epoxy substrate, a glass composite substrate, a paper phenol substrate, conforming to various standards such as FR-1, FR-3, FR-4, CEM-3, or E668, Examples include paper epoxy substrates, green epoxy substrates, and BT resin substrates.
Other substrates applicable to the present invention include, for example, a substrate made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless steel (these metals on the surface) Aluminium oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (zircon), magnesium oxide (magnesia), aluminum titanate, barium titanate, titanic acid Lead (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide (beryllia), silicon oxide (silica), Silicon carbide (silicon carbide), silicon nitride (silicon A substrate made of ceramics such as zinc oxide, boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel, or spodumene (may be a substrate having such ceramics on the surface); PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylenedimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, Polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, epoxy resin, acrylic resin, Teflon (registered trademark), thermoplastic A substrate made of a resin such as a lastomer or a liquid crystal polymer (may be a substrate having such a resin on its surface); a semiconductor substrate such as silicon, germanium, or gallium arsenide; a glass substrate; tin oxide, zinc oxide, ITO, Or a substrate on which an electrode material such as ATO is formed; a gel sheet such as αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel), or γGEL (gamma gel) (which is a registered trademark of Taika Co., Ltd.) It is done.

[Electronic parts]
The electronic component of the present invention is an electronic component having the above-mentioned substrate with a cured film. Thus, a flexible electronic component is obtained using the board | substrate with a cured film which has a film substrate of this invention. Moreover, a semiconductor electronic component can be obtained by using the substrate with a cured film having the silicon wafer substrate of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples. The names and abbreviations of amino compounds (a1), acid anhydrides (a2) and (a2 ′), epoxy compounds (B), solvents (C) and epoxy curing agents (D) used in Examples and Comparative Examples are shown. . This abbreviation is used in the following description.

<Compound (a1)>
AEE: 2- (2-aminoethoxy) ethanol APE-OH: 2- (4-aminophenyl) ethanol

<Acid anhydrides (a2) and (a2 ′)>
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride PMDA: pyromellitic dianhydride TMA: trimellitic anhydride MA: maleic anhydride

<Epoxy compound (B)>
VG3101L: Trade name “Techmore VG3101L” (manufactured by Mitsui Chemicals, Inc.)
EP828EL: Trade name “Epicoat 828EL” (manufactured by Yuka Shell Epoxy Co., Ltd.)

<Reaction solvent or solvent (C)>
ETNL: Ethanol EDM: Diethylene glycol methyl ethyl ether GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone

<Epoxy curing agent (D)>
TMA: trimellitic anhydride CA: citraconic anhydride

[Synthesis Example 1]
A 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging charge port and a nitrogen gas inlet was charged with 330.0 g of ETNL and 135.5 g (1.290 mol) of AEE as a reaction solvent. Then, 200.0 g (0.645 mol) of ODPA was added with stirring under a dry nitrogen stream, and the mixture was refluxed at 130 ° C. for 5 hours under normal pressure. Thereafter, ETNL was distilled off, 600 g of acetone was added, and the mixture was stirred at room temperature for 2 hours. After stirring, the mixture was filtered and the residue was dried under reduced pressure. As a result, 220.5 g of an imidized product represented by the formula (s1-2) was obtained.
40.62 g (0.084 mol) of an imidized product represented by the formula (s1-2), 57.0 g of EDM and 16.4 g (0.168 mol) of MA, a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas introduction A reaction solution charged in a 300 ml four-necked flask equipped with a reflux condenser with a connected mouth, stirred at 100 ° C. under normal pressure for 3 hours, and containing an ester compound represented by formula (s1-3) as a main component (A) -1 was obtained.
The rotational viscosity of the reaction solution (A) -1 measured at 25 ° C. using an E-type rotational viscometer (VISCONIC ELD manufactured by TOKYO KEIKI) was 45.0 mPa · s. The solid content concentration was 50% by weight.

[Synthesis Example 2]
A 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet was charged with 180.0 g of GBL and 40.3 g (0.384 mol) of AEE as a reaction solvent. Then, 41.9 g (0.192 mol) of PMDA was added with stirring under a dry nitrogen stream and refluxed at 130 ° C. for 4 hours under normal pressure. Thereafter, the temperature was lowered to 40 ° C., and 37.7 g (0.384 mol) of MA was added. Thereafter, the mixture is stirred at 100 ° C. for 6 hours, and contains an ester compound represented by the formula (s2-4) as a main component, an amide acid represented by the formula (s2-1), and represented by the formula (s2-3). The liquid mixture (A) -2 containing the ester compound and imidized product represented by the formula (s2-2) was obtained.
The rotational viscosity of the liquid mixture (A) -2 measured at 25 ° C. using an E-type rotational viscometer (VISCONIC ELD manufactured by TOKYO KEIKI) was 35.0 mPa · s. The solid content concentration was 40% by weight.

[Synthesis Examples 3 to 6]
In Synthesis Example 2, mixed solutions (A) -3 to (A) -6 were obtained in the same manner as in Synthesis Example 2 except that the reaction raw materials and the reaction solvent were charged as shown in Table 1. Table 1 shows the viscosity and solid content concentration at 25 ° C.

[Synthesis Example 7]
In a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, EDM 90.0 g and NMP 90.0 g were placed as reaction solvents, and AEE 41.9 g (. 398 mol) was charged, 78.1 g (0.796 mol) of MA was added with stirring under a dry nitrogen stream, and the mixture was refluxed at 130 ° C. for 4 hours under normal pressure. Thereby, the liquid mixture containing the ester compound represented by Formula (s7-1) and the ester compound represented by Formula (s7-2) including the ester compound represented by Formula (s7-3) as a main component. (A) -7 was obtained. Table 1 shows the viscosity and solid content concentration at 25 ° C.

[Synthesis Example 8]
In Synthesis Example 7, a mixed liquid (A) -8 was obtained in the same manner as in Synthesis Example 7 except that the reaction raw materials and the reaction solvent were charged as shown in Table 1. Table 1 shows the viscosity and solid content concentration at 25 ° C.

[Comparative Synthesis Example 1]
A 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet was charged with 180.0 g of GBL and 17.6 g (0.168 mol) of AEE as a reaction solvent. Then, 36.6 g (0.168 mol) of PMDA was added with stirring in a dry nitrogen stream, and the mixture was refluxed at 130 ° C. for 4 hours under normal pressure. Thereafter, the temperature was lowered to 40 ° C., and 65.9 g (0.672 mol) of MA was added. When the mixture was stirred at 100 ° C. for 6 hours and then returned to room temperature, insolubilization occurred in the flask, and a uniform solution could not be obtained.
The results of Synthesis Examples 1 to 8 and Comparative Synthesis Example 1 are shown in Table 1.

Further, when the molar number n _a1 amino compounds used in the reaction (a1), an acid anhydride (a2) and the total number of moles of the (a2 ') was n _a2, the molar ratio (n _a1 / n _a2 ) Is shown in Table 2.

[Example 1]
29.8 g of the reaction liquid (A) -1 obtained in Synthesis Example 1 was added to a 300 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging charge port and a reflux condenser connected with a nitrogen gas inlet. 45.0 g of EDM as the solvent (C), 22.4 g of VG3101L as the epoxy compound (B), and 2.7 g of TMA as the epoxy curing agent (D) were mixed in that order. This was stirred at room temperature for 3 hours to obtain a thermosetting composition. The rotational viscosity of the thermosetting composition measured at 25 ° C. using an E-type rotational viscometer (VISCONIC ELD manufactured by TOKYO KEIKI) was 12.3 mPa · s. The solid content concentration was 40% by weight.

[Examples 2 to 12, Comparative Examples 1 to 3]
In Example 1, a thermosetting composition was prepared in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 3. Table 3 shows the viscosity and solid content concentration at 25 ° C.
The results of Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 3 above.

Measurement and evaluation of each physical property of the obtained thermosetting composition were performed by the following methods.
(I) Storage Stability In order to check the storage stability of the thermosetting composition, the viscosity after storage for 60 days was measured under freezing (−20 ° C.). The viscosity of the thermosetting composition was measured at 25 ° C. using an E-type rotational viscometer (VISCONIC ELD manufactured by TOKYO KEIKI). If the difference in viscosity before and after storage for 60 days is less than 5%, AA is set, and if it is 5% or more, BB is set.

(Ii) Inkjet drawing properties The inkjet composition of the thermosetting composition was applied using an inkjet coating apparatus DMP-2831 (model number) manufactured by FUJIFILM Dimatix and an inkjet head having a discharge amount of 10 pl.
A glass epoxy resin double-sided copper-clad board with a thickness of 1.5 mm is used as the printed circuit board, the printing setting is a line application with a dot width of 30 microns, a dot pitch of 5 cm, a piezo voltage of 18 V, and the number of printing layers is one layer. The discharge temperature was 25 ° C. and the drive frequency was 5 kHz. Under this condition, one drop can be discharged at 9.0 to 9.5 pl.
After completing the inkjet application, the line width of the coating film formed on the substrate was observed with an optical microscope. Next, the substrate was dried on a hot plate at 80 ° C. for 5 minutes, and then heated in an oven at 180 ° C. for 90 minutes to obtain a cured film formed in a line shape. Using a stylus-type film thickness meter α step 200 manufactured by KLA-Tencor Japan, the arithmetic average value of three measured values was defined as the film thickness.

(Iii) Adhesion between the copper foil and the cured film formed from the thermosetting composition The thickness is the same print setting as in the above (ii) inkjet drawing evaluation except that the number of print layers is three. The thermosetting composition was applied to a glossy surface of a 35 μm Nikko Metal copper foil (model number BHY-22B-T). After coating, the film was dried on a hot plate at 80 ° C. for 5 minutes, and then heated in an oven at 180 ° C. for 90 minutes to form a cured film.
A support substrate with an adhesive is attached to the surface of the substrate on which the cured film is formed, a copper tape is etched with a masking tape having a width of 2.5 mm on the back surface of the copper foil, and a width of 2. on the cured film. A 5 mm copper foil was prepared.
After peeling off the masking tape, a trigger for peeling is created at the interface between the copper foil and the cured film, and the copper foil is peeled off in the 180 ° direction by the tensile tester EZGraph manufactured by Shimadzu Corporation. Was measured.

(Iv) Electrical characteristics evaluation (volume resistivity, dielectric strength)
The thermosetting composition was applied on a chromium substrate with the same print settings as in the evaluation of (iii) adhesion. After application, the film was dried for 5 minutes on a hot plate at 80 ° C., and then heated in an oven at 180 ° C. for 90 minutes to form a cured film having a thickness of 2 μm. Then, aluminum was vapor-deposited on the cured film and the electrode was created. Volume resistivity and dielectric strength were measured using a digital superinsulation / microammeter DSM-8104 (manufactured by Hioki Electric Co., Ltd.).

(V) Heat resistance evaluation (5% weight loss temperature)
The thermosetting composition was applied on a glass substrate with the same print settings as in the above (iii) adhesion evaluation. After application, the film was dried on a hot plate at 80 ° C. for 5 minutes, and then heated in an oven at 180 ° C. for 90 minutes to form a cured film. Using a differential thermogravimetric simultaneous measurement device (Seiko Instruments, SSC5200), the 5% weight loss temperature of a cured film formed on a glass substrate was measured with a knife.
The measurement conditions are shown below.
・ Sample weight: 5mg
-Temperature rise start temperature: 30 ° C
-Temperature rise end temperature: 500 ° C
・ Raising rate: 10 ° C / min
・ Atmosphere: In the air

(Vi) Alkali solution resistance Substrate [(Mitsui Chemicals Co., Ltd.) Neoprex NEX- with copper foil (thickness 12.5 μm) laminated on polyimide with the same printing settings as in (iii) Adhesion evaluation above A square pattern of 40 mm × 40 mm was formed on the copper foil surface of [13FE (trade name)]. This was dried on an 80 ° C. hot plate for 5 minutes, and then heated in an oven at 180 ° C. for 90 minutes to form a cured film.
The obtained cured film was immersed in a 2N aqueous NaOH solution at room temperature for 15 minutes, washed with water and dried at 60 ° C. for 30 minutes. This was evaluated with an optical microscope as alkali solution resistance according to the following evaluation criteria.
AA: Abnormalities such as infiltration and peeling are not observed at the interface between the cured film and the copper foil.
BB: Abnormalities such as infiltration and peeling were observed at the interface between the cured film and the copper foil.

(Vii) Warp test PI tape with adhesive (model number KY6240, manufactured by Toa Flex Co., Ltd.), leaving a 30 × 30 mm central part of a 40 × 40 mm base material (Kapton 200H (thickness 50 μm) manufactured by Toray DuPont Co., Ltd.) ) Was fixed on a glass substrate (50 × 50 mm), ink-jet printing was performed on the substrate with the same print settings as in the evaluation of (iii) adhesion, and dried at 80 ° C. for 5 minutes. This was returned to room temperature, the PI tape was peeled off, and heated in an oven at 180 ° C. for 90 minutes to form a cured film. This was returned to room temperature and allowed to stand at 20 ° C. and 60% humidity for 16 hours (the thickness of the cured film at this time was 10 ± 2 μm). This base material was placed on a horizontal plane, the heights of warping at the four corners from the flat surface were measured, and the arithmetic average value was taken as the amount of warping.

  Table 4 summarizes the results of Examples 1-12 and Comparative Examples 1-3.

In all the examples, the difference in viscosity before and after storage for 60 days was less than 5%, and there was no problem in storage stability. In each of the examples, the line width was almost the same as that applied, the linearity of the edge of the line was good, and the line had a sufficient thickness. The examples all showed sufficient adhesion strength values, and the adhesion was good. All the examples showed good insulating properties. In all the examples, the 5% weight loss temperature was 300 ° C. or more, and good heat resistance was exhibited. In all the examples, abnormalities such as infiltration and peeling were not observed, and the chemical resistance was good. In all the examples, the warpage value was within 5.0 mm, and the warpage was low.
As is clear from the above results, a cured film having a thickness exceeding 2 μm is obtained from the thermosetting composition of the present invention, and further, the cured film has adhesion, electrical properties, heat resistance, and alkali solution resistance. All the evaluations regarding low warpage were also good.

  Examples of the utilization method of the present invention include an insulating film for a flexible printed wiring board, a rigid printed wiring board, or a semiconductor, and an electronic component using the insulating film.

Claims (15)

(A) (i) an amino compound (a1) represented by the general formula (1),
An amide acid obtained by reacting the acid anhydride (a2), and (ii) the amide acid or an imidized product thereof,
Furthermore, at least one carboxyl group-containing compound selected from an ester compound obtained by reacting with an acid anhydride (a2 ′) ( excluding a compound represented by the following general formula (1 ′)) ,
(B) An inkjet ink comprising a thermosetting composition containing an epoxy compound.

[In Formula (1), Z is a divalent organic group. ]

[In the formula (1 ′),
R ¹ is an aryl having 6 to 20 carbon atoms which may have a substituent, a cycloalkyl having 5 to 20 carbon atoms which may have a substituent, or a monovalent group represented by the following general formula (2 ′). The substituent is carboxyl, hydroxyl or alkyl having 1 to 14 carbons;

(In the formula (2 ′), R ⁴ is alkylene having 2 to 8 carbon atoms, R ⁵ is hydrogen or a monovalent group represented by the following general formula (3 ′), and n is 1 to 10 (It is an integer.)

(In the formula (3 ′), R ⁶ is a divalent group represented by any one of the following formulas (a) to (g).)
R ² is a divalent group represented by any of the following formulas (a) to (g);
R ³ is a monovalent group represented by the following general formula (4 ′).

(In the formula (4 ′), R ⁷ is alkylene having 2 to 8 carbon atoms, R ⁸ is hydrogen or a monovalent group represented by the following general formula (5 ′), and n is 1 to 10 (It is an integer.)

(In the formula (5 ′), R ⁹ is a divalent group represented by any one of the following formulas (a) to (g).)

The inkjet ink according to claim 1, wherein the acid anhydrides (a2) and (a2 ') are each independently at least one selected from dicarboxylic acid anhydrides and tetracarboxylic dianhydrides. The dicarboxylic acid anhydride is a compound represented by the general formula (2),
Tetracarboxylic dianhydride is a compound represented by the general formula (3),
The ink-jet ink according to claim 2.

[In Formula (2), X is

Either
In formula (3), Y is

{Where R ¹ is a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ -

R ² is any one of a single bond, —O—, —CO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —. It is. }. ] The carboxyl group-containing compound (A) is at least one selected from compounds represented by general formulas (i-1) to (i-3) and (ii-1) to (ii-8). The ink-jet ink according to 3.

[In formulas (i-1) to (i-3) and (ii-1) to (ii-8), X has the same meaning as X in formula (2), and Y represents Y in formula (3). Z is synonymous with Z in formula (1), A is synonymous with X in formula (2), or the following formula (where Y is Y in formula (3) Which is synonymous.) . ]

Z in the general formula (1) is an alkylene having 1 to 20 carbon atoms, a group in which any methylene in the alkylene is replaced with an aromatic group, or — (CH ₂ CH ₂ —O) _n —CH ₂ CH ₂ The inkjet ink according to any one of claims 1 to 4, which is a group represented by-(n is an integer of 1 to 10). The epoxy compound (B) is alkylene glycol diglycidyl ether, 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, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N -Diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and at least one selected from the group consisting of compounds represented by formulas (B1) to (B4) A kind of compound, The inkjet ink according to any one of Motomeko 1-5.

[In formula (B1), p is an integer of 1-50. ] The inkjet ink according to any one of claims 1 to 6, further comprising a solvent (C). Solvent (C) is ethyl lactate, ethanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether , Ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, Triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene group Cole monoethyl ether, propylene glycol monomethyl ether, triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 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-dimethylacetamide, A solvent containing at least one selected from N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and γ-butyrolactone , The inkjet ink according to Motomeko 7. The inkjet ink according to any one of claims 1 to 8, further comprising an epoxy curing agent (D) other than the carboxyl group-containing compound (A). The epoxy curing agent (D) is at least one selected from acid anhydride curing agents, phenol resin curing agents, amine adducts, polycarboxylic acid curing agents, polyamine curing agents and catalytic curing agents. Item 10. The inkjet ink according to Item 9. The cured film or pattern shape obtained through the process of apply | coating the inkjet ink as described in any one of Claims 1-10 with the inkjet coating method, and forming the coating film, and the process of hardening-processing this coating film Cured film. Step of ink-jet ink according to any one of claims 1 to 10 to form a coating film by an inkjet coating method, and a step of curing the coating film, the cured film or patterned cured film Forming method. The board | substrate with a cured film which has a film substrate and the cured film or pattern-shaped cured film formed on the board | substrate by the formation method of Claim 12 . A substrate with a cured film, comprising: a silicon wafer substrate; and a cured film or a patterned cured film formed on the substrate by the forming method according to claim 12 . The electronic component which has a board | substrate with a cured film of Claim 13 or Claim 14 .