JP5641010B2 - Thermosetting composition - Google Patents

Description

  The present invention relates to a thermosetting composition, for example, a thermosetting composition containing a silicon compound (A) and / or a silicon compound (A ′) for forming an insulating film layer in the manufacture of electronic components, and the thermosetting composition. The present invention relates to a polyimide film formed using an object, a film substrate on which the polyimide film is formed, and an electronic component having the film substrate.

Polyimide is a material widely used in the field of electronic communication because it has excellent heat resistance and electrical insulation [see, for example, Patent Document 1, Patent Document 2, and Patent Document 3].
In the case of using polyimide as a desired pattern film, conventionally, it has been common to form a pattern using etching or photosensitive polyimide. However, in recent years, methods for forming a desired pattern film with a dispenser have been studied. Yes.

  Various thermosetting compositions have been proposed. Usually, the polyimide thermosetting composition is a polyimide precursor polyamic acid or a solvent-soluble polyimide solution. However, since the solid content of polyamic acid or soluble polyimide is a relatively high polymer, in order to prepare an optimum viscosity as a thermosetting composition for a dispenser, the solid content in the composition is increased by increasing the proportion of the solvent. It is necessary to reduce the concentration. However, there is a problem that a desired sufficient film thickness cannot be obtained. Further, when the proportion of the solvent increases, there is a problem that curing shrinkage of the film tends to occur and warping of the substrate occurs. As a thermosetting composition having low warpage, a polyamide-imide resin having flexibility has been proposed. However, a polyamide-imide resin usually has insufficient heat resistance and electrical insulation as compared with a polyimide resin.

JP 2000-039714 A JP 2003-238683 A JP 2004-094118 A

  Under the circumstances described above, there has been a demand for a thermosetting composition that can form a relatively thick polyimide film (100 μm or more) with heat resistance, electrical insulation, and low warpage by dispenser application.

In view of the above situation, the present inventors have provided a thermosetting composition containing at least one silicon compound (A) and / or at least one silicon compound (A ′), and further a polymer compound (B). The thermosetting composition containing, the thermosetting composition containing the alkenyl substituted nadiimide (C), and the thermosetting composition further containing the solvent (D) were found.
The present invention provides the following thermosetting composition and the like.

  [1] Silicon compound (A) obtained by using compound (a1) having two or more acid anhydride groups and monoamine (a2), and compound (a1 ′) having one acid anhydride group and diamine A thermosetting composition having a viscosity of 51 to 50000 mPa · s (25 ° C.), comprising at least one selected from silicon compounds (A ′) obtained using (a2 ′).

（一般式（１）中、Ｘは炭素数２〜１００の四価の有機基であり、一般式（２）中、Ｒ^１、Ｒ^２及びＲ^３は独立して、水素、ハロゲンまたは一価の有機基であり、それらは同一または異なっていてもよく、Ｙは、炭素数１〜２０の二価の有機基である。） [2] The compound (a1) having two or more acid anhydride groups is a tetracarboxylic dianhydride represented by the general formula (1), and the monoamine (a2) is represented by the general formula (2). The thermosetting composition according to the above [1], which is an aminosilicon compound.

(In General Formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms. In General Formula (2), R ¹ , R ² and R ³ are independently hydrogen, halogen or monovalent. These may be the same or different, and Y is a divalent organic group having 1 to 20 carbon atoms.)

[3] The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic. Acid dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3,3 '-Diphenylsulfonetetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 2, 2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] Hexafluorop Lopan dianhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5- One or more selected from the group consisting of cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride,
The aminosilicon compound is selected from the group consisting of paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, and aminopropyltriethoxysilane. One or more,
The thermosetting composition according to the above [2].

（一般式（３）中、Ｘは、炭素数２〜１００の四価の有機基であり、Ｒ^１、Ｒ^２及びＲ^３は独立して、水素、ハロゲンまたは一価の有機基であり、それらは同一または異なっていてもよく、Ｙは、炭素数１〜２０の二価の有機基である。） [4] The thermosetting composition according to the above [1], wherein the silicon compound (A) is a silicon amide acid (A) represented by the general formula (3).

(In General Formula (3), X is a tetravalent organic group having 2 to 100 carbon atoms, R ¹ , R ² and R ³ are independently hydrogen, halogen or a monovalent organic group, They may be the same or different, and Y is a divalent organic group having 1 to 20 carbon atoms.)

（一般式(4-1)、(4-2)及び(4-3)中、Ｒ^１、Ｒ^２及びＲ^３は独立して、水素、ハロゲンまたは一価の有機基であり、Ｒ^１、Ｒ^２及びＲ^３の内の少なくとも一つは、炭素数１〜２０のアルコキシを含み、ａは、１〜２０の整数である。） [5] The thermosetting property as described in [4] above, wherein the silicon amic acid (A) is a silicon amic acid represented by the general formula (4-1), (4-2) or (4-3). Composition.

(Formula (4-1), (4-2) and (4-3), R ^1, R ² and R ³ are independently hydrogen, halogen or a monovalent organic group, R ^1, At least one of R ² and R ³ includes alkoxy having 1 to 20 carbons, and a is an integer of 1 to 20)

  [6] The above [1] to [5], wherein the ratio of the compound (a1) having two or more acid anhydride groups to the monoamine (a2) is 1 mol: 0.5 to 8.0 mol. The thermosetting composition according to any one of the above.

（一般式（１’）中、Ｒ^１、Ｒ^２及びＲ^３は独立して、水素、ハロゲンまたは一価の有機基であり、それらは同一または異なっていてもよく、Ｙ’は、炭素数１〜２０の三価の有機基であり、一般式（２’）中、Ｘ’は炭素数２〜１００の二価の有機基である。） [7] The compound (a1 ′) having one acid anhydride group is a dicarboxylic acid anhydride represented by the general formula (1 ′), and the diamine (a2 ′) is represented by the general formula (2 ′). The thermosetting composition according to any one of the above [1] to [6], which is a diamine represented by

(In the general formula (1 ′), R ¹ , R ² and R ³ are independently hydrogen, halogen or a monovalent organic group, and they may be the same or different, and Y ′ represents the number of carbon atoms. (It is a 1-20 trivalent organic group, and X 'is a C2-C100 divalent organic group in general formula (2').)

[8] The dicarboxylic acid anhydride of the general formula (1 ′) is p- (trimethoxysilyl) phenyl succinic anhydride, p- (triethoxysilyl) phenyl succinic anhydride, m- (trimethoxysilyl). One or more selected from the group consisting of phenyl succinic anhydride, m- (triethoxysilyl) phenyl succinic anhydride, trimethoxysilylpropyl succinic anhydride and triethoxysilylpropyl succinic anhydride,
The diamine of the general formula (2 ′) is p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-1,2-diphenylethane, 4, 4'-diamino-1,3-diphenylpropane, 2,2-bis (4-aminophenyl) propane, bis (4-amino-3-methylphenyl) methane, 1,2-bis- (4-amino-3) -Methylphenyl) ethane, bis (4-amino-2-methylphenyl) methane, 1,2-bis- (4-amino-2-methylphenyl) ethane, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-di Aminodiphenyl-2,2′-propane, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 1,4-bis [(4-aminophenyl) methyl] benzene, 1,4-bis (4- Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] fluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] biphenyl, 1,3-bis [4- (4-aminobenzyl) phenyl] propane 1,6-bis [4- (4-aminobenzyl) phenyl] hexane, 5-phenylmethyl-1,3-diaminobenzene, 5 [4- (4-alkylcyclohexyl) phenyl] methyl-1,3-diaminobenzene, 5- [4- (4- (4-alkylcyclohexyl) cyclohexyl) phenyl] methyl-1,3-diaminobenzene, 5- [ ((Alkylcyclohexyl) ethylcyclohexyl) phenyl] methyl-1,3-diaminobenzene, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) ) Phenyl] -4-alkylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-alkylcyclohexane, 1, selected from the group consisting of 3-bis (3-aminopropyl) -tetramethyldisiloxane One or more,
The thermosetting composition according to [7] above.

（一般式（３’）中、Ｒ^１、Ｒ^２及びＲ^３は独立して、水素、ハロゲンまたは一価の有機基であり、それらは同一または異なっていてもよく、Ｙ’は、炭素数１〜２０の三価の有機基であり、Ｘ’は炭素数２〜１００の二価の有機基である。） [9] The thermosetting composition according to any one of [1] to [5], wherein the silicon compound (A ′) is a silicon amide acid (A ′) represented by the general formula (3 ′). object.

(In General Formula (3 ′), R ¹ , R ^2, and R ³ are independently hydrogen, halogen, or a monovalent organic group, and they may be the same or different, and Y ′ is the number of carbon atoms. 1 to 20 trivalent organic groups, and X ′ is a divalent organic group having 2 to 100 carbon atoms.)

（一般式(4'-1)、(4'-2)、(4'-3)、(4'-4)及び(4'-5)中、Ｒ^１、Ｒ^２及びＲ^３は独立して、水素、ハロゲンまたは一価の有機基であり、それらは同一または異なっていてもよく、Ｒ^１、Ｒ^２及びＲ^３の内の少なくとも一つは、炭素数１〜２０のアルコキシを含み、ａは、１〜１９の整数であり、一般式(4'-3)のＲは炭素数２〜３０の有機基であり、一般式(4'-4)のＲは水素又は炭素数１〜２０のアルキルである。） [10] The silicon amic acid (A ′) is represented by the general formula (4′-1), (4′-2), (4′-3), (4′-4) or (4′-5). The thermosetting composition according to [9] above, which is represented by silicon amic acid (A ′).

(In the general formulas (4'-1), (4'-2), (4'-3), (4'-4) and (4'-5), R ¹ , R ² and R ³ are independently Hydrogen, halogen or a monovalent organic group, which may be the same or different, and at least one of R ¹ , R ² and R ³ contains an alkoxy having 1 to 20 carbon atoms; a is an integer of 1 to 19, R in the general formula (4′-3) is an organic group having 2 to 30 carbon atoms, and R in the general formula (4′-4) is hydrogen or 1 to 19 carbon atoms. 20 alkyls.)

  [11] The above [1] to [10], wherein the ratio of the compound (a1 ′) having one acid anhydride group to the diamine (a2 ′) is 0.5 to 8.0 mol: 1 mol. ] The thermosetting composition in any one of.

  [12] The thermosetting composition according to any one of [1] to [11], further including a polymer compound (B).

  [13] The thermosetting composition according to the above [12], wherein the polymer compound (B) is at least one selected from polyamic acid and polyimide.

  [14] The thermosetting composition according to the above [12] or [13], wherein the polymer compound (B) has a weight average molecular weight of 1,000 to 5,000.

  [15] The thermosetting composition according to any one of [1] to [14], further including an alkenyl-substituted nadiimide (C).

（一般式（５）中、Ｒ^１およびＲ^２はそれぞれ独立に、水素、炭素数１〜１２のアルキル、炭素数３〜６のアルケニル、炭素数５〜８のシクロアルキル、炭素数６〜１２のアリールまたはベンジルのいずれかであり、ｎは１〜２の整数であり、
ｎ＝１のとき、Ｒ^３は水素、炭素数１〜１２のアルキル、炭素数１〜１２のヒドロキシアルキル、炭素数５〜８のシクロアルキル、炭素数６〜１２のアリール、ベンジル、−｛（Ｃ_ｑＨ_２ｑ）Ｏ_ｔ（Ｃ_ｒＨ_２ｒＯ）_ｕＣ_ｓＨ_２ｓＸ｝（ここで、ｑ、ｒ、ｓはそれぞれ独立に選ばれた２〜６の整数、ｔは０または１の整数及びｕは１〜３０の整数、Ｘは水素または水酸基である）で表されるポリオキシアルキレンアルキル、−（Ｒ）_ａ−Ｃ_６Ｈ_４−Ｒ^４（ここで、ａは０または１の整数、Ｒは炭素数１〜４のアルキレン、Ｒ^４は水素もしくは炭素数１〜４のアルキルを表す）で表される基、−Ｃ_６Ｈ_４−Ｔ−Ｃ_６Ｈ_５（ここで、Ｔは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｓ−もしくはＳＯ_２−である）で表される基、またはこれらの基の芳香環に直結した１〜３個の水素が水酸基で置き換えられた基であり、
ｎ＝２のとき、Ｒ^３は−Ｃ_ｐＨ_２ｐ−（ここで、ｐは２〜２０の整数）で表されるアルキレン、炭素数５〜８のシクロアルキレン、−｛（Ｃ_ｑＨ_２ｑＯ）_ｔ（Ｃ_ｒＨ_２ｒＯ）_ｕＣ_ｓＨ_２ｓ｝−（ここで、ｑ、ｒ、ｓはそれぞれ独立に２〜６の整数、ｔは０または１の整数及びｕは１〜３０の整数である）で表されるポリオキシアルキレン、炭素数６〜１２のアリーレン、−（Ｒ）_ａ−Ｃ_６Ｈ_４−Ｒ^５−（ここで、ａは０または１の整数、Ｒ及びＲ^５は独立に選ばれた炭素数１〜４のアルキレンである）で表される基、−Ｃ_６Ｈ_４−Ｔ−Ｃ_６Ｈ_４−（ここで、Ｔは−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＯ−、−Ｏ−、−ＯＣ_６Ｈ_４Ｃ（ＣＨ_３）_２Ｃ_６Ｈ_４Ｏ−、−Ｓ−、−ＳＯ_２−）で表される基、またはこれらの基の芳香環に直結する１〜３個の水素が水酸基で置き換えられた基である。） [16] The thermosetting composition according to [15] above, wherein the alkenyl-substituted nadiimide (C) is a compound represented by the general formula (5).

(In General Formula (5), R ¹ and R ² 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. Any one of aryl and benzyl, n is an integer of 1 to 2,
When n = 1, R ³ 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, s is an integer of from 2 to 6 selected independently, t is an integer of 0 or 1 And u is an integer of 1 to 30, X is hydrogen or a hydroxyl group, and-(R) _a -C ₆ H ₄ -R ⁴ (where a is an integer of 0 or 1) , R is alkylene having 1 to 4 carbon atoms, R ⁴ is 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 - and is) A group represented by or a group 1 to 3 hydrogens directly bonded to the aromatic ring is replaced with a hydroxyl group of these groups,
When n = 2, R ³ is alkylene represented by —C _p H _2p — (where 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 and u is 1 to 30 integer Is a polyoxyalkylene, an arylene having 6 to 12 carbon atoms,-(R) _a -C ₆ H ₄ -R ^5- (where a is an integer of 0 or 1, R and R ⁵ are groups represented by independently is selected alkylene having 1 to 4 carbon _{atoms), -C 6 H 4 -T-} C 6 H 4 - ( where, 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 -) , a group represented by Or it is a group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced by a hydroxyl group. )

  [17] The thermosetting composition according to the above [16], wherein in the general formula (5), n is 2.

[18] In the general formula (5), n is 2, and R ³ is alkylene represented by —C _p H _2p — (where p is an integer of 2 to 10), — (R) _a A group represented by —C ₆ H ₄ —R ⁵ — (wherein a is an integer of 0 or 1 and R and R ⁵ are independently selected alkylene having 1 to 4 carbon atoms), or —C ₆ H ₄ —TC ₆ H ₄ — (where 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 - is a group represented by), the [16] the thermosetting composition.

[19] In the general formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons,
The thermosetting composition according to [16] above, wherein n is 2, and R ³ is — (CH ₂ ) ₆ —, a group represented by formula (6) or a group represented by formula (7). .

  [20] The above general formula (5), including at least one alkenyl-substituted nadiimide compound (C) in which n is 1 and at least one alkenyl-substituted nadiimide compound (C) in which n is 2 [16] The thermosetting composition according to [16].

[21] In the general formula (5), n is 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,-{( in _{C q H 2q) O t (} C r H 2r O) u C s H 2s + 1} ( where, q, r, s is an integer of from 2 to 6 selected independently, t is an integer of 0 or 1 and u is an integer of 1 to 30, polyoxyalkylene alkyl represented by-(R) _a -C ₆ H ₄ -R ⁴ (where a is an integer of 0 or 1 and R is a carbon number of 1 to 4 alkylene, R ⁴ represents hydrogen or alkyl having 1 to 4 carbon atoms, respectively, or —C ₆ H ₄ —TC ₆ H ₅ (wherein T is —CH ₂ —, A group represented by —C (CH ₃ ) ₂ —, —CO—, —S— or SO ₂ —. The thermosetting composition according to the above [16], comprising at least one alkenyl-substituted nadiimide compound (C) and at least one alkenyl-substituted nadiimide compound (C) wherein n is 2.

[22] In the general formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 1, and R ³ is alkyl having 1 to 12 carbons or carbon. At least one alkenyl-substituted nadiimide compound (C) that is cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, or benzyl, and at least one alkenyl-substituted nadiimide compound (C) in which n is 2. The thermosetting composition according to [16] above, comprising:

[23] In the general formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 1, and R ³ is alkyl or carbon having 1 to 12 carbons. At least one alkenyl-substituted nadiimide compound (C) that is aryl having 6 to 12, R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 2, R ³ -[CH ₂ ) _6- , the group represented by formula (6) or the alkenyl-substituted nadiimide compound (C) which is a group represented by formula (7), Thermosetting composition.

  [24] The thermosetting composition according to any one of [1] to [23], further including a solvent (D).

  [25] The solvent (D) 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. The thermosetting composition according to the above [24], which is at least one selected from the group consisting of acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone and γ-butyrolactone. .

  [26] A polyimide film obtained by applying the thermosetting composition described in any one of [1] to [25] above by a dispenser coating method to form a coating film, and then curing the coating film. Or a patterned polyimide film.

  [27] A step of applying the thermosetting composition described in any of [1] to [25] above by a dispenser coating method to form a coating film, and curing the coating film to form a polyimide film. A method for forming a polyimide film or a patterned polyimide film, which includes a step of forming.

  [28] A film substrate having a polyimide film or a patterned polyimide film formed on the substrate by the method described in [27] above.

  [29] An electronic component having the film substrate described in [28].

  [30] A silicon wafer film substrate having a polyimide film or a patterned polyimide film formed on the substrate by the method described in [27] above.

  [31] An electronic component having the silicon wafer substrate described in [28].

  When the thermosetting composition according to a preferred embodiment of the present invention is used, a polyimide film having a relatively thick film thickness can be formed by one application. Moreover, the polyimide film formed from the thermosetting composition according to a preferred embodiment of the present invention has, for example, high heat resistance and high electrical insulation, and improves the reliability and yield of electronic components.

The present invention provides a thermosetting composition containing a silicon compound (A) and / or a silicon compound (A ′), a method for forming a polyimide film using the thermosetting composition, and the like. The thermosetting composition of the present invention may be colorless or colored.
The thermosetting composition includes at least one silicon compound (A) and / or a thermosetting composition containing at least one silicon compound (A), and further includes a polymer compound (B). Product, further a thermosetting composition containing alkenyl-substituted nadiimide (C), and further a thermosetting composition containing solvent (D).

The silicon compound (A) can be obtained using at least the compound (a1) having two or more acid anhydride groups and the monoamine (a2). For example, a product obtained by reacting them (silicon Amic acid (A)) may be used. For example, these may be a compound forming a salt. Compound (a1) having two or more acid anhydride groups and monoamine (a2) may be used. Any silicon compound can be used as long as it can be obtained by using it.
Further, silicon in the silicon compound (A) may be derived from the compound (a1) having two or more acid anhydride groups, may be derived from the monoamine (a2), or may be derived from both. In the following, the silicon compound (A) is obtained using silicon derived from the monoamine (a2). Examples of the compound (a1) having two or more acid anhydride groups having silicon include, for example, Examples thereof include compounds described in JP-A-61-205285, JP-A-5-27245, JP-A-5-320172, and the like.

The silicon compound (A ′) can be obtained using at least the compound (a1 ′) having one acid anhydride group and the diamine (a2 ′). For example, the silicon compound (A ′) can be obtained by reacting them. It may be a product (silicon amic acid (A ′)), for example, a compound forming a salt thereof, a compound (a1 ′) having one acid anhydride group and a diamine If it is a silicon compound which can be obtained using (a2 '), it will not be limited to these.
Further, silicon in the silicon compound (A ′) may be derived from the compound (a1 ′) having one acid anhydride group, from the diamine (a2 ′), or from both. . Hereinafter, the silicon compound (A ′) is obtained using silicon derived from the compound (a1 ′) having one acid anhydride group. Examples of the diamine (a2 ′) having silicon include, for example, Examples thereof include siloxane-based diamines represented by the general formula (XV).

1 Silicon amide acid (A) and Silicon amide acid (A ')
The silicon amic acid (A) contained in the thermosetting composition of the present invention is obtained by a production method described below using at least a compound (a1) having two or more acid anhydride groups and a monoamine (a2). However, it is not limited to the silicon amide acid obtained by the said manufacturing method. Examples of the silicon amide acid (A) include compounds represented by the above general formula (3), and compounds represented by the above general formula (4-1), (4-2) or (4-3) preferable.
Further, the silicon amide acid (A ′) contained in the thermosetting composition of the present invention is described below using at least a compound (a1 ′) having one acid anhydride group and a diamine (a2 ′). However, it is not limited to the silicon amide acid obtained by the said manufacturing method. Examples of the silicon amide acid (A ′) include compounds represented by the general formula (3 ′), and the general formulas (4′-1), (4′-2), (4′-3), A compound represented by (4′-4) or (4′-5) is preferred.

1.1 Reaction conditions for obtaining silicon amic acid (A) and silicon amic acid (A ′) The silicon amic acid (A) that can be used in the present invention is a compound (a1) having two or more acid anhydride groups. ) It is preferably obtained by reacting 0.5 to 8.0 moles of monoamine (a2) with respect to 1 mole. Moreover, it is more preferable that it is a thing obtained by making 1.0-4.0 mol monoamine (a2) react with respect to 1 mol of compounds (a1) which has two or more acid anhydride groups. More preferably, it is obtained by reacting 1.5 to 2.5 mol of monoamine (a2) with respect to 1 mol of compound (a1) having two or more acid anhydride groups.
The silicon amic acid (A ′) that can be used in the present invention is a compound (a1) having one acid anhydride group of 0.5 to 8.0 mol relative to 1 mol of diamine (a2 ′). It is preferable that it is obtained by reacting '). Moreover, it is more preferable that it is a thing obtained by making the compound (a1 ') which has one 1.0-4.0 mol acid anhydride group with respect to 1 mol diamine (a2'). More preferably, it is obtained by reacting 1 mol of diamine (a2 ′) with a compound (a1 ′) having one acid anhydride group of 1.5 to 2.5 mol.

1.1 (1) Reaction solvent The solvent used to obtain the silicon amide acids (A) and (A ′) of the present invention is not particularly limited as long as the compound can be synthesized. For example, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, γ-butyrolactone, N- And methyl-2-pyrrolidone and N, N-dimethylacetamide.
These reaction solvents can be used alone or as a mixed solvent of two or more. In addition to the reaction solvent, other solvents can be mixed and used.

  When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight in total of the compound (a1) having two or more acid anhydride groups and the monoamine (a2), or the compound having one acid anhydride group (a1 ′ ) And diamine (a2 ′) are preferably used in an amount of 100 parts by weight or more based on a total of 100 parts by weight because the reaction proceeds smoothly. The reaction is preferably carried out at 0 to 100 ° C. (preferably 8 to 70 ° C.) for 0.2 to 20 hours (preferably 2 to 10 hours).

1.1 (2) The order of addition to the reaction system and the order of addition of reaction raw materials to the reaction system are not particularly limited. That is, for silicon amic acid (A), compound (a1) having two or more acid anhydride groups and monoamine (a2) are simultaneously added to the reaction solvent. After monoamine (a2) is dissolved in the reaction solvent, the acid is added. Any method such as adding the compound (a1) having two or more anhydride groups or adding the monoamine (a2) to the compound (a1) having two or more acid anhydride groups can be used.
For silicon amic acid (A ′), compound (a1 ′) having one acid anhydride group and diamine (a2 ′) are simultaneously added to the reaction solvent, and diamine (a2 ′) is dissolved in the reaction solvent. It is possible to use any method such as adding a compound (a1 ′) having one acid anhydride group and adding a diamine (a2 ′) to a compound (a1 ′) having one acid anhydride group. it can.

1.2 Superiority of silicon amide acid (A) and silicon amide acid (A ′) Silicon amide acid (A) acts as a silane coupling agent when used in combination with an epoxy resin or a phenol resin to react with a metal or It is known that since the complex is formed, the adhesion of the film is increased and the solder crack resistance is improved. In addition, when silicon amic acid (A ′) is used in combination with an epoxy resin or a phenol resin, it acts as a silane coupling agent to form a reaction or complex with the metal, so that the adhesion of the film is increased and the solder crack resistance is increased. Is expected to improve.
Furthermore, as a result of intensive studies by the present inventors, silicon amic acid (A) is a thermosetting compound that can be hydrolyzed and dehydrated by heating to become a solid product (polyimide) having an imide bond. I found out. It was also found that silicon amic acid (A ′) is a thermosetting compound that can be hydrolyzed and dehydrated by heating to become a solid product (polyimide) having an imide bond.
Since a film is obtained by three-dimensional crosslinking of a silicon compound, it is easier to process than a conventional linear polyimide. In addition, since it exhibits good heat resistance and less voids and cracks during curing, it has excellent characteristics as a matrix resin for molding materials and laminated materials.

1.3 Explanation of Components for Obtaining Silicon Amic Acids (A) and (A ′) Hereinafter, compounds having two or more acid anhydride groups that can be used to obtain silicon amic acid (A) (A1) and monoamine (a2) will be described. Furthermore, a compound (a1 ′) having one acid anhydride group and a diamine (a2 ′) that can be used to obtain silicon amide acid (A ′) will be described.

1.3 (1) Compound (a1) having two or more acid anhydride groups
Examples of the compound (a1) having two or more acid anhydride groups used in the present invention include tetracarboxylic dianhydrides represented by the above general formula (1).
Specific examples of the compound (a1) having two or more acid anhydride groups used in the present invention have an anhydride group such as a styrene-maleic anhydride copolymer and a methyl methacrylate-maleic anhydride copolymer. Examples include a copolymer of a radical polymerizable monomer and another radical polymerizable monomer, tetracarboxylic dianhydride, and the like. Examples of the tetracarboxylic dianhydride include 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′. , 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylethertetracarboxylic dianhydride 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), ethanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran- 3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohe Sen-1,2-dicarboxylic anhydride and the like, and specific examples thereof include tetracarboxylic dianhydride such as compounds represented by the following formula (b1-1) ~ (b1-73).

  Among the above specific examples of the compound having two or more acid anhydrides, styrene-maleic anhydride copolymer, formula (b1-1), (b1-5), (b1-6), (b1-7), Since the compounds represented by (b1-8), (b1-9), (b1-14), (b1-18), and (b1-20) have high solubility in solvents, a high concentration varnish can be prepared. preferable. Further, depending on the use of the thermosetting composition, high transparency is required. In such a case, a styrene-maleic anhydride copolymer, formula (b1-6), (b1-7), It is particularly preferable to use a compound represented by (b1-8), (b1-9), (b1-14), (b1-18) or the like.

  In addition, the compounds having two or more acid anhydride groups described above may be used singly or in combination of two or more.

1.3 (2) Monoamine (a2)
The monoamine (a2) used in the present invention is not particularly limited, and examples of the monoamine (a2) preferably used in the present invention include aminosilicon compounds represented by the above general formula (2).
Specific examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyl. Triethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyl Examples include trimethoxysilane, m-aminophenyltriethoxysilane, and m-aminophenylmethyldiethoxysilane.

  Of these, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane, 3- Aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are preferred, and 3-aminopropyltriethoxysilane is particularly preferred.

  These monoamines can be used alone or in combination of two or more.

1.3 (3) Compound (a1 ′) having one acid anhydride group
The compound (a1 ′) having one acid anhydride group used in the present invention is not particularly limited, but the compound (a1 ′) having one acid anhydride group preferably used in the present invention includes the above general formula. The dicarboxylic acid anhydride represented by (1 ') is mentioned.
Specific examples include trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilylpropyl succinic anhydride, trimethoxysilylbutyl succinic anhydride. , Triethoxysilylbutyl succinic anhydride, methyldiethoxysilylbutyl succinic anhydride, p- (trimethoxysilyl) phenyl succinic anhydride, p- (triethoxysilyl) phenyl succinic anhydride, p- (methyl Dimethoxysilyl) phenyl succinic anhydride, p- (methyldiethoxysilyl) phenyl succinic anhydride, m- (trimethoxysilyl) pheny Succinate anhydrase hydride, m- (triethoxysilyl) phenyl succinate anhydrase hydride, m- and the like (methyldiethoxysilyl) phenyl succinate anhydrase hydride.

  Among these, p- (trimethoxysilyl) phenyl succinic anhydride, p- (triethoxysilyl) phenyl succinic anhydride, m- (trimethoxysilyl) phenyl from the point that the durability of the obtained film is excellent. Succinic anhydrides, m- (triethoxysilyl) phenyl succinic anhydrides, trimethoxysilylpropyl succinic anhydrides and triethoxysilylpropyl succinic anhydrides are preferred, and triethoxysilylpropyl succinic anhydrides are particularly preferred.

  These compounds having one acid anhydride group can be used singly or in combination of two or more.

1.3 (4) Diamine (a2 ′)
Examples of the diamine (a2 ′) used in the present invention include diamines represented by the general formula (2 ′).
The diamine (a2 ′) used in the present invention is not particularly limited as long as it has two amino groups. For example, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4 ′. -Diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-1,3-diphenylpropane, 2,2-bis (4-aminophenyl) propane, bis (4-amino -3-methylphenyl) methane, 1,2-bis- (4-amino-3-methylphenyl) ethane, bis (4-amino-2-methylphenyl) methane, 1,2-bis- (4-amino-) 2-methylphenyl) ethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4 ′ -Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-2,2'-propane, 1,4-diaminocyclohexane, 4,4'-diamino Dicyclohexylmethane, 1,4-bis [(4-aminophenyl) methyl] benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-Aminophenoxy) phenyl] biphenyl, 1,3-bis [4- (4-aminobenzyl) phenyl] propaprop 1,6-bis [4- (4-aminobenzyl) phenyl] hexane, 5-phenylmethyl-1,3-diaminobenzene, 5- [4- (4-alkylcyclohexyl) phenyl] methyl-1,3- Diaminobenzene, 5- [4- (4- (4-alkylcyclohexyl) cyclohexyl) phenyl] methyl-1,3-diaminobenzene, 5-[((alkylcyclohexyl) ethylcyclohexyl) phenyl] methyl-1,3-diamino Benzene, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-alkylcyclohexane, 1,1-bis [4- (4-Aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl]- Examples include 4-alkylcyclohexane and 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and compounds represented by the following general formulas (II) to (VIII).

（一般式（II）中、
Ａ^１は、−（ＣＨ_２）_ｍ−であり、ここでｍは１〜６の整数であり、
一般式（IV）及び（VI）〜（VIII）中、
Ａ^１は、単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−（ＣＨ_２）_ｍ−、−Ｏ−（ＣＨ_２）_ｍ−Ｏ−、−Ｓ−（ＣＨ_２）_ｍ−Ｓ−であり、ここでｍは１〜６の整数であり、
Ａ^２は、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または炭素数１〜３のアルキレンであり、
シクロヘキサン環またはベンゼン環に結合している水素は、−Ｆ、−ＣＨ_３と置き換えられていてもよい。）

(In general formula (II),
A ¹ is — (CH ₂ ) _m —, where m is an integer of 1 to 6,
In the general formulas (IV) and (VI) to (VIII),
A ¹ is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C ( CF ₃ ) ₂ —, — (CH ₂ ) _m —, —O— (CH ₂ ) _m —O—, —S— (CH ₂ ) _m —S—, wherein m is an integer of 1 to 6. Yes,
A ² is a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or alkylene having 1 to 3 carbon atoms,
Hydrogen bonded to a cyclohexane ring or a benzene ring may be replaced with -F or -CH ₃ . )

  Examples of the diamine represented by the general formula (II) include diamines represented by the following formulas (II-1) to (II-3).

  Examples of the diamine represented by the general formula (III) include diamines represented by the following formulas (III-1) and (III-2).

  Examples of the diamine represented by the general formula (IV) include diamines represented by the following formulas (IV-1) to (IV-3).

  Examples of the diamine represented by the general formula (V) include diamines represented by the following formulas (V-1) to (V-5).

  Examples of the diamine represented by the general formula (VI) include diamines represented by the following formulas (VI-1) to (VI-30).

  Examples of the diamine represented by the general formula (VII) include diamines represented by the following formulas (VII-1) to (VII-6).

  Examples of the diamine represented by the general formula (VIII) include diamines represented by the following formulas (VIII-1) to (VIII-11).

  Among the specific examples of the diamines (a2 ′) represented by the general formulas (II) to (VIII), more preferably, the formulas (V-1) to (V-5) and the formulas (VI-1) to (VI) VI-12), formula (VI-26), formula (VI-27), formula (VII-1), formula (VII-2), formula (VII-6), formula (VIII-1) to (VIII- The diamine represented by 5) is mentioned, More preferably, the diamine represented by Formula (V-6), Formula (V-7), Formula (VI-1)-(VI-12) is mentioned.

  Examples of the diamine (a2 ′) used in the present invention further include diamines represented by the following general formula (IX).

（一般式（IX）中、
Ａ^３は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−または−（ＣＨ_２）_ｍ−（式中、ｍは１〜６の整数である）であり、
Ｒ^６は、ステロイド骨格を有する基、下記一般式（Ｘ）で表される基、または、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炭素数１〜３０のアルキル、もしくは該位置関係がメタのときは炭素数１〜３０のアルキルまたはフェニルであり、
該アルキルにおいては、任意の−ＣＨ_２−が−ＣＦ_２−、−ＣＨＦ−、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、−ＣＨ_３が−ＣＨ_２Ｆ、−ＣＨＦ_２または−ＣＦ_３で置き換えられていてもよく
該フェニルの環形成炭素に結合している水素は、−Ｆ、−ＣＨ_３、−ＯＣＨ_３、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３と置き換えられていてもよい。）

(In general formula (IX),
A ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _m — (wherein m is an integer of 1 to 6). ,
R ⁶ is a group having a steroid skeleton, a group represented by the following general formula (X), or a C 1-30 when the positional relationship between two amino groups bonded to the benzene ring is para-position Alkyl, or alkyl having 1 to 30 carbon atoms or phenyl when the positional relationship is meta,
In the alkyl, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, and —CH ₃ may be —CH _{3. 2} F, —CHF ₂ or —CF ₃ may be substituted. The hydrogen bonded to the ring-forming carbon of the phenyl is —F, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF _2. Alternatively, it may be replaced with —OCF ₃ . )

（一般式（Ｘ）中、
Ａ^４およびＡ^５はそれぞれ独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−または炭素数１〜１２のアルキレンであり、
Ｒ^７およびＲ^８はそれぞれ独立して、−Ｆまたは−ＣＨ_３であり、
環Ｓは１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、
Ｒ^９は−Ｈ、−Ｆ、炭素数１〜３０のアルキル、炭素数１〜３０のフッ素置換アルキル、炭素数１〜３０のアルコキシ、−ＣＮ、−ＯＣＨ_２Ｆ、−ＯＣＨＦ_２または−ＯＣＦ_３であり、
ａおよびｂはそれぞれ独立して０〜４の整数を表し、
ｃ、ｄおよびｅはそれぞれ独立して０〜３の整数を表し、ｅが２または３であるとき複数の環Ｓは同一の基であっても異なる基であってもよく、
ｆおよびｇはそれぞれ独立して０〜２の整数を表し、かつ
ｃ＋ｄ＋ｅ≧１である。）

(In general formula (X),
A ⁴ and A ⁵ are each independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons;
R ⁷ and R ⁸ are each independently —F or —CH ₃ ;
Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl;
R ⁹ is —H, —F, alkyl having 1 to 30 carbons, fluorine-substituted alkyl having 1 to 30 carbons, alkoxy having 1 to 30 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF _3. And
a and b each independently represents an integer of 0 to 4;
c, d and e each independently represent an integer of 0 to 3, and when e is 2 or 3, the plurality of rings S may be the same group or different groups,
f and g each independently represent an integer of 0 to 2 and c + d + e ≧ 1. )

In the general formula (IX), 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 are preferably bonded to the 3rd and 5th positions or the 2nd and 5th positions, respectively, when the bonding position of “R ⁶ -A ³ —” is the 1st position.
Examples of the diamine represented by the general formula (IX) include diamines represented by the following general formulas (IX-1) to (IX-11).

In the general formulas (IX-1), (IX-2), (IX-7) and (IX-8), R ¹⁸ is an organic group having 2 to 30 carbon atoms. 12 alkyl or C3-C12 alkoxy is preferable, and C5-C12 alkyl or C5-C12 alkoxy is more preferable. In the general formulas (IX-3) to (IX-6) and (IX-9) to (IX-11), R ¹⁹ is —H or an organic group having 1 to 30 carbon atoms. Of these, alkyl having 1 to 10 carbon atoms or alkoxy having 1 to 10 carbon atoms is preferable, and alkyl having 3 to 10 carbon atoms or alkoxy having 3 to 10 carbon atoms is more preferable.

  Examples of the diamine represented by the general formula (IX) further include diamines represented by the following general formulas (IX-12) to (IX-17).

In the general formulas (IX-12) to (IX-15), R ²⁰ is —H or an organic group having 1 to 30 carbon atoms, preferably an alkyl group having 4 to 16 carbon atoms, and an alkyl group having 6 to 16 carbon atoms. Further preferred. In general formulas (IX-16) and (IX-17), R ²¹ is —H or 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. Further preferred.

  Examples of the diamine represented by the general formula (IX) further include diamines represented by the following general formulas (IX-18) to (IX-38).

General formula (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31) , (IX-36) and (IX-37), R ²² represents —H or an organic group having 1 to 30 carbon atoms, preferably alkyl having 1 to 12 carbon atoms or alkoxy having 1 to 12 carbon atoms, More preferred is alkyl having 3 to 12 or alkoxy having 3 to 12 carbon atoms. In addition, the above general formulas (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX-32) 35) and (IX-38), R ²³ represents —H, —F, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF _3. More preferably, alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons is used. In the above general formulas (IX-33) and (IX-34), A ⁹ is alkylene having 1 to 12 carbons.

  Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-39) to (IX-48).

  Of the diamines (a2 ′) represented by the general formula (IX), diamines represented by the general formulas (IX-1) to (IX-11) are preferable, and the general formulas (IX-2) and (IX-4) ), (IX-5) and (IX-6) are more preferred.

  Examples of the diamine (a2 ′) used in the present invention further include compounds represented by the following general formulas (XI) and (XII).

（一般式（XI）と（XII）中、
Ｒ^１０は−Ｈまたは−ＣＨ_３であり、
Ｒ^１１はそれぞれ独立して、−Ｈまたは炭素数１〜２０のアルキルもしくはアルケニルであり、
Ａ^６はそれぞれ独立して、単結合、−Ｃ（＝Ｏ）−または−ＣＨ_２−であり、
Ｒ^１３およびＲ^１４はそれぞれ独立して、−Ｈ、炭素数１〜２０のアルキルまたはフェニルである。）

(In general formulas (XI) and (XII),
R ¹⁰ is —H or —CH ₃ ;
Each R ¹¹ is independently —H or an alkyl or alkenyl having 1 to 20 carbon atoms;
Each A ⁶ is independently a single bond, —C (═O) — or —CH ₂ —;
R ¹³ and R ¹⁴ are each independently —H, C 1-20 alkyl or phenyl. )

In the general formula (XI), it is preferable that one of the two “NH ₂ —Ph—A ⁶ —O—” is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position. The two amino groups are each bonded to the phenyl ring carbon, and preferably bonded to the meta position or the para position with respect to the bonding position of A ⁶ .
Examples of the diamine represented by the general formula (XI) include diamines represented by the following formulas (XI-1) to (XI-4).

In the general formula (XII), two “NH ₂ — (R ¹⁴ —) Ph—A ⁶ —O—” are each bonded to the phenyl ring carbon, but preferably to the carbon to which the steroid nucleus is bonded. On the other hand, it is bonded to carbon in the meta or 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 diamine represented by the general formula (XII) include diamines represented by the following formulas (XII-1) to (XII-8).

  Examples of the diamine (a2 ′) used in the present invention further include compounds represented by the following general formulas (XIII) and (XIV).

（一般式（XIII）中、
Ｒ^１５は−Ｈまたは炭素数１〜２０のアルキルであり、該アルキルのうち炭素数２〜２０のアルキルの任意の−ＣＨ_２−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、
Ａ^７はそれぞれ独立して−Ｏ−または炭素数１〜６のアルキレンであり、
Ａ^８は単結合または炭素数１〜３のアルキレンであり、
環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり、
ｈは０または１である。）

(In general formula (XIII),
R ¹⁵ is —H or alkyl having 1 to 20 carbons, and any —CH ₂ — in the alkyl having 2 to 20 carbons is —O—, —CH═CH— or —C≡C. -May be replaced by
Each A ⁷ is independently —O— or alkylene having 1 to 6 carbons;
A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms,
Ring T is 1,4-phenylene or 1,4-cyclohexylene,
h is 0 or 1. )

（一般式（XIV）中、
Ｒ^１６は炭素数６〜２２のアルキルであり、
Ｒ^１７は−Ｈまたは炭素数１〜２２のアルキルであり、
Ａ^７はそれぞれ独立して−Ｏ−または炭素数１〜６のアルキレンである。）

(In general formula (XIV),
R ¹⁶ is alkyl having 6 to 22 carbon atoms,
R ¹⁷ is —H or alkyl having 1 to 22 carbons;
A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms. )

In the general formula (XIII), the two amino groups are respectively bonded onto carbons of the benzene ring, it is preferably bonded in the meta or para to A ^7.
Examples of the diamine represented by the general formula (XIII) include diamines represented by the following general formulas (XIII-1) to (XIII-9).

In the general formulas (XIII-1) to (XIII-3), R ²⁴ is preferably —H and alkyl having 1 to 20 carbon atoms, and in (XIII-4) to (XIII-9), R ²⁵ is —H, More preferred is alkyl having 1 to 10 carbon atoms.

In the general formula (XIV), the two amino groups are respectively bonded onto carbons of the benzene ring, it is preferably bonded in the meta or para position with respect to A ^7.
Examples of the diamine represented by the general formula (XIV) include diamines represented by the following general formulas (XIV-1) to (XIV-3).

In the general formulas (XIV-1) to (XIV-3), R ²⁶ is an organic group having 2 to 30 carbon atoms. Among these, alkyl having 6 to 20 carbon atoms is preferable, and R ²⁷ is 2 carbon atoms. Is an organic group having ˜30, and among these, —H or alkyl having 1 to 10 carbon atoms is more preferable.

  As described above, as the diamine (a2 ′) used in the present invention, for example, diamines represented by the general formulas (II) to (XIV) can be used, but diamines other than these diamines can also be used. . For example, a naphthalene diamine having a naphthalene structure, a fluorene diamine having a fluorene structure, a siloxane diamine having a siloxane bond, or the like can be used alone or mixed with another diamine.

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

（上記一般（XV）式中、Ｒ^３およびＲ^４は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｒ^５は独立してはメチレン、フェニレンまたはアルキル置換されたフェニレンであり、ｘは独立して１〜６の整数であり、ｙは１〜７０の整数である。ここで、より好ましいｙは１〜１５の整数である。）

(In the above general formula (XV), R ³ and R ⁴ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁵ is independently methylene, phenylene or alkyl-substituted phenylene, x Is independently an integer of 1 to 6, and y is an integer of 1 to 70. Here, more preferable y is an integer of 1 to 15.)

  Furthermore, preferably, diamines represented by the following general formulas (XVI-1) to (XVI-8) can be used as the diamine (a2 ′) used in the present invention.

（上記一般式（XVI-1）〜（XVI-8）中、Ｒ^３０およびＲ^３１は独立して炭素数３〜２０のアルキルである。）

(In the general formulas (XVI-1) to (XVI-8), R ³⁰ and R ³¹ are each independently alkyl having 3 to 20 carbon atoms.)

In addition, the diamine (a2 ′) that can be used in the present invention is not limited to the diamine in the present specification, and various other forms of diamine may be used within the scope of achieving the object of the present invention. Can do.
Moreover, the diamine (a2 ') which can be used by this invention can be used individually by 1 type or in combination of 2 or more types. That is, as a combination of two or more kinds, the above diamines, the above diamine and other diamines, or diamines other than the above diamines can be used.

  Further, depending on the use of the thermosetting composition, high transparency is required. In such a case, 3, 3′-diaminodiphenyl sulfone and y = 1 to 15 in the general formula (XV) are used. It is particularly preferred to use an integer diamine.

2 Polymer compound (B)
The polymer compound (B) that can be further contained in the thermosetting composition of the present invention includes polyamic acid, soluble polyimide, polyamide, polyamideimide, polyamic acid ester, polyester, acrylic acid polymer, acrylate polymer, polyvinyl alcohol, poly Although it is high molecular compounds, such as oxyethylene, it is not limited to this. Preferably, it is a polyimide-based polymer compound such as polyamic acid or soluble polyimide, and for example, polyamic acid described in Japanese Patent Application No. 2006-235336, or imidized polymer thereof can be preferably mentioned, but is not limited thereto. Is not to be done.
The polyamic acid can be obtained using at least the compound (b1) having two or more acid anhydride groups, the diamine (b2), and the monoamine (b3), but is limited to the polyamic acid obtained by the production method. Is not to be done.

  Below, the compound (b1), diamine (b2), and monoamine (b3) which have two or more acid anhydride groups which can be used in order to obtain a high molecular compound (B) are demonstrated.

2.1 Compound (b1) having two or more acid anhydride groups
As a specific example of the compound (b1) having two or more acid anhydride groups used in the present invention, the compound (b1) having two or more acid anhydride groups that can be used to obtain the silicon amic acid (A) described above. The thing similar to a compound (a1) can be used.
The compound (b1) having two or more acid anhydride groups may be the same as or different from the compound (a1) having two or more acid anhydride groups. In addition, the compounds having an acid anhydride group described above may be used singly or in combination of two or more.

2.2 Diamine (b2)
As a specific example of the diamine (b2) used in the present invention, the same diamine (a2 ′) that can be used for obtaining the silicon amic acid (A ′) can be used.
The diamine (b2) may be the same as or different from the diamine (a2 ′). In addition, the diamines described above may be used alone or in combination of two or more.

2.3 Monoamine (b3)
As a specific example of the monoamine (b3) used in the present invention, the same monoamine (a2) that can be used to obtain the silicon amic acid (A) described above can be used.
The monoamine (b3) may be the same as or different from the monoamine (a2). Moreover, the monoamines described above may be used singly or in combination of two or more.

2.4 Reaction Conditions of Polyamic Acid The polyamic acid that can be used in the present invention is 0.05 to 0.8 mol of diamine (b2) with respect to 1 mol of compound (b1) having two or more acid anhydride groups. ), 0.4 to 1.9 mol of monoamine (b3) is preferably obtained. Moreover, 0.1-0.6 mol diamine (b2) and 0.8-1.8 mol monoamine (b3) are reacted with respect to 1 mol of the compound (b1) having two or more acid anhydride groups. It is more preferable that it is obtained. More preferably, 0.15 to 0.35 mol of diamine (b2) and 1.3 to 1.7 mol of monoamine (b3) with respect to 1 mol of compound (b1) having two or more acid anhydride groups. It is obtained by reacting.

2.4 (1) Reaction solvent The solvent used to obtain the polyamic acid that can be used in the present invention is the same as the solvent that can be used to obtain the silicon amic acid (A) or (A ′) described above. Can be used. The reaction solvent can be used alone or as a mixed solvent of two or more. In addition to the reaction solvent, other solvents can be mixed and used.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the compound (b1) having two or more acid anhydride groups, the diamine (b2) and the monoamine (b3), because the reaction proceeds smoothly. . The reaction is preferably carried out at 0 to 100 ° C. (preferably 8 to 70 ° C.) for 0.2 to 20 hours (preferably 2 to 10 hours).

2.4 (2) The order of addition to the reaction system and the order of addition of reaction raw materials to the reaction system are not particularly limited. That is, the compound (b1) having two or more acid anhydride groups, the diamine (b2), and the monoamine (b3) are simultaneously added to the reaction solvent, and the diamine (b2) and the monoamine (b3) are dissolved in the reaction solvent. The compound (b1) having two or more acid anhydride groups is added later, the compound (b1) having two or more acid anhydride groups and the monoamine (b3) are reacted in advance, and then the diamine (b2) is added. In any method, a compound (b1) having two or more acid anhydride groups is reacted in advance with a diamine (b2) to synthesize a copolymer, and then a monoamine (b3) is added to the copolymer. Can be used.

2.5 Weight average molecular weight of the polymer compound (B) The polymer compound (B) having a weight average molecular weight of 1,000 to 200,000 is particularly excellent in solubility in a solvent and is preferred as a thermosetting composition. In the present invention, in order to further improve the “solubility” of the polymer compound (B) in the solvent, the weight average molecular weight is preferably 1,000 to 100,000, and 1,000 to 50,000. More preferably.
And it is especially preferable that the weight average molecular weights of a high molecular compound (B) are 1,000-20,000. The polymer compound (B) having a weight average molecular weight of 1,000 or more does not evaporate by heat treatment, is chemically and mechanically stable, and has a weight average molecular weight of 20,000 or less. Since (B) can improve the solubility with respect to a solvent, it is possible to enlarge the film thickness of the coating film obtained, and is because it can be preferably used as a thermosetting composition.

  The weight average molecular weight of the polymer compound (B) can be measured by a gel permeation chromatography (GPC) method. Specifically, the obtained polymer compound (B) was diluted with tetrahydrofuran (THF) or the like so as to have a concentration of about 1% by weight, and columns G4000HXL, G3000HXL, G2500HXL and G2000HXL manufactured by Tosoh Corporation were used. It can be determined by measuring by gel permeation chromatography (GPC) using THF as a developing agent and converting to polystyrene.

3 Alkenyl-substituted nadiimide compound (C)
The alkenyl-substituted nadiimide compound (C) contained in the thermosetting composition of the present invention is a compound having at least one alkenyl-substituted nadiimide structure in the molecule, preferably an alkenyl-substituted compound represented by the above general formula (5). Although a nadiimide compound can be mentioned, it is not limited to this.

  The alkenyl-substituted nadiimide compound (C) includes an alkenyl-substituted nadiimide compound in which n is 1 (c1: hereinafter referred to simply as “alkenyl-substituted nadiimide”) and an alkenyl-substituted nadiimide compound in which n is 2 (c2: Hereinafter, it may be simply referred to as “bisalkenyl-substituted nadiimide”.

3.1 Alkenyl-substituted nadiimide (c1)
Specific examples of the alkenyl-substituted nadiimide compound in which n is 1 used in the present invention include the following.

Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
Methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-hydroxy-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2′-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2′-hydroxyethyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2′-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- (2 ′, 2′-dimethyl-3′-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2 ′, 2′-dimethyl-3′-hydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2 ′, 3′-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2 ′, 3′-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3′-hydroxy-1′-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4′-hydroxy-cyclohexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- (4′-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4′-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4′-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (4′-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3′-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (3′-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {2 ′-(2′-hydroxyethoxy) ethyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

Also,
N- {2 ′-(2′-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {2 ′-(2′-hydroxyethoxy) ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {2 ′-(2′-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- [2 ′-{2 ′-(2 ″ -hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- [2 ′-{2 ′-(2 ″ -hydroxyethoxy) ethoxy} ethyl] -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- [2 ′-{2 ′-(2 ″ -hydroxyethoxy) ethoxy} ethyl] -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- {4 ′-(4′-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
And oligomers thereof.

  These alkenyl-substituted nadiimides (c1) may be used alone or as a mixture thereof.

Preferred as the alkenyl-substituted nadiimide (c1) is N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

Also,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

Also,
N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

More preferred as the alkenyl-substituted nadiimide (c1) is
N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

Also,
N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and the like can be mentioned.

3.2 Bisalkenyl-substituted nadiimide (c2)
Further, specific examples of the alkenyl-substituted nadiimide compound in which n is 2 used in the present invention include the following.

N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
And oligomers thereof.

Also,
1,2-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
1,2-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
1,2-bis {3 ′-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane,
Bis [2 ′-{3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
Bis [2 ′-{3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether,
1,4-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,
1,4-bis {3 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,
And oligomers thereof.

Also,
N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
And oligomers thereof.

Also,
2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4 ′-{4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4 ′-{4 ′-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
And oligomers thereof.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
And oligomers thereof.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
1,6-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -3-hydroxy-hexane,
1,12-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -3,6-dihydroxy-dodecane,
1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane,
1,5-bis {3 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} -3-hydroxy-pentane,
1,4-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-benzene,
And oligomers thereof.

Also,
1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene,
N, N′-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
And oligomers thereof.

Also,
2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2′-hydroxy-phenoxy} phenyl] propane,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane,
Bis {3- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -4-hydroxy-phenyl} ether,
Bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone,
1,1,1-tri {4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)} phenoxymethylpropane,
N, N ′, N ″ -tri (ethylenemethallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) isocyanurate,
And oligomers thereof.

  Further, the following one containing an asymmetric alkylene-phenylene group may be used.

  These bisalkenyl-substituted nadiimides (c2) may be used alone or as a mixture thereof.

As the bisalkenyl-substituted nadiimide (c2), preferred is N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Also,
N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4 ′-{4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4 ′-{4 ′-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
And bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

Also,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,
And bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone.

Also,
And bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone.

As the bisalkenyl-substituted nadiimide (c2), more preferred are
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Also,
N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N ′-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) and the like.

Also,
2,2-bis [4 ′-{4 ′-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4 ′-{4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
2,2-bis [4 ′-{4 ′-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane,
Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane,
And bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane.

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

  Since the preferred alkenyl-substituted nadiimide compound (C) of the present invention is a low molecular weight imide monomer having a bulky structure, it is soluble in most organic solvents, and even if it is stored in a solution state for a long period of time, crystals are precipitated. And can be used stably without gelation. Moreover, a polyimide having a three-dimensional cross-linking structure is formed by heating, and the cured polyimide exhibits good heat resistance, mechanical properties, electrical properties, and chemical resistance.

4 Solvent (D)
The thermosetting composition of the present invention comprises, for example, silicon amic acid (A) and / or (A ′), if necessary, a polymer compound (B) and an alkenyl-substituted nadiimide compound (C) dissolved in a solvent (D). Can be obtained. Therefore, the solvent contained in the thermosetting composition of the present invention dissolves the silicon amide acid (A) and / or (A ′), and if necessary, the polymer compound (B) and the alkenyl-substituted nadiimide compound (C). The solvent is not particularly limited as long as it can be used. Moreover, even if it is a solvent that does not dissolve silicon amide acid (A), silicon amide acid (A ′), polymer compound (B), and alkenyl-substituted nadiimide compound (C) as necessary, it is mixed with other solvents. It can be used as a solvent (D) contained in the thermosetting composition.

  Specific examples of the solvent (D) contained in the thermosetting composition include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethyl Sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyrolactone, ethyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene Glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether Ether, triethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethyl malonate, ethanol, 2-propanol, Dioxane, ethylene glycol, propylene glycol, glycerin, cyclohexanone and the like can be mentioned.

Among these, 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 Preferable examples include acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, and γ-butyrolactone.
Only 1 type may be used for a solvent (D), and 2 or more types may be mixed and used for it.

5 Solid content concentration of the thermosetting composition of the present invention In the present invention, the silicon amide acid (A) and / or silicon amide acid (A '), the polymer compound (B) and the alkenyl-substituted nadiimide in the thermosetting composition The total concentration (solid content concentration) of compound (C) is not particularly limited, but is preferably 45 to 99% by weight, more preferably 50 to 90% by weight, and still more preferably 55 to 85% by weight. These concentration ranges are preferable because the thickness of the film obtained by one dispenser application is optimized. Furthermore, it is preferable because curing shrinkage of the film and warping of the substrate hardly occur.

  In the present invention, the concentration of the polymer compound (B) in the thermosetting composition is not particularly limited, but is preferably 0 to 50% by weight, and more preferably 0 to 30% by weight. These concentration ranges are preferable because good characteristics can be imparted as an insulating film.

  In the present invention, the concentration of the alkenyl-substituted nadiimide compound (C) in the thermosetting composition is not particularly limited, but is preferably 0 to 70% by weight, and more preferably 0 to 60% by weight. These concentration ranges are preferable because good characteristics can be imparted as an insulating film.

  When used as a thermosetting composition, the higher the concentration of silicon amide acid (A) and / or silicon amide acid (A '), polymer compound (B) and alkenyl-substituted nadiimide compound (C), the higher the polyimide film obtained. This is preferable because the film thickness is increased. If it is said density | concentration range, it can use preferably as a thermosetting composition which can form a polyimide film with a big film thickness.

6 Additives to be added to the thermosetting composition of the present invention The thermosetting composition of the present invention is composed of silicon amide acid (A) and / or silicon amide acid (A '), and if necessary, a polymer compound (B). , An alkenyl-substituted nadiimide compound (C) and, if necessary, a solvent (D).
Furthermore, depending on the intended properties, the thermosetting composition of the present invention may be used as an epoxy resin, an acrylic resin, a surfactant, an antistatic agent, a coupling agent, trimellitic acid, etc. Addition of epoxy curing agents, aminosilicon compounds, pH adjusters, rust inhibitors, antiseptics, antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, water-soluble polymers, pigments, dyes, etc. An agent can be selected and added as necessary, and can be obtained by uniformly mixing and dissolving them.

6 (1) Epoxy Resin The thermosetting composition of the present invention may further contain an epoxy resin. The epoxy resin contained in the thermosetting composition of the present invention is not particularly limited as long as it has oxirane or oxetane, but a compound having two or more oxiranes is preferable.

  In the present invention, the concentration of the epoxy resin in the thermosetting composition is not particularly limited, but is preferably 0.1 to 60% by weight, and more preferably 1 to 40% by weight. Within this concentration range, the heat resistance, chemical resistance and flatness of the coating film formed from the thermosetting composition are good.

  Examples of the epoxy resin include a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a polymer of a monomer having an oxirane, and a copolymer of a monomer having an oxirane and another monomer. Is mentioned.

Specific examples of the monomer having oxirane include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methylglycidyl (meth) acrylate.
Specific examples of the monomer having an oxirane and other monomers copolymerized include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, iso-butyl (meth) acrylate, tert-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, benzyl methacrylate-glycidyl methacrylate copolymer, Examples include n-butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer. be able to. When the thermosetting composition of this invention contains these epoxy resins, since the heat resistance of the coating film formed from the thermosetting composition becomes favorable, it is preferable.

Specific examples of the epoxy resin that can be included in the thermosetting composition of the present invention include trade names “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 190P”. ”,“ Epicoat 191P ”(manufactured by Yuka Shell Epoxy Co., Ltd.), product names“ Epicoat 1004 ”,“ Epicoat 1256 ”(manufactured by Japan Epoxy Resin Co., Ltd.), product name“ Araldite CY177 ”, products Name “Araldite CY184” (manufactured by Ciba-Geigy Japan), trade names “Celoxide 2021P”, “Celoxide 3000”, “EHPE-3150” (Daicel Chemical Industries, Ltd.), trade name “Techmore VG3101L” (Mitsui Chemicals) N, N, N ′, N′-tetraglycidyl-m-xylenedi Min, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', such as N'- tetraglycidyl-4,4'-diaminodiphenylmethane and the like.
Among these, the trade name “Araldite CY184”, the trade name “Celoxide 2021P”, the trade name “Techmore VG3101L”, and the trade name “Epicoat 828” are preferable because the flatness of the resulting polyimide film is particularly good.

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

6 (2) Acrylic Resin The thermosetting composition of the present invention may further contain an acrylic resin. The acrylic resin contained in the thermosetting composition is not particularly limited as long as it has an acrylic group or a methacrylic group.

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

  Examples of the acrylic resin 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.

  Specific examples of the monofunctional polymerizable monomer having hydroxyl include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or 1,4-cyclohexanedimethanol mono A (meth) acrylate etc. can be mentioned. Among these, 4-hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are particularly preferable because the formed film is 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, 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] , Mono [2- (meth) acryloyloxyethyl maleate], or 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, or dipentaerythritol diacrylate Or the like can be mentioned acrylate.

Specific examples of trifunctional or higher polyfunctional (meth) acrylates are trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Examples thereof include ethylene oxide-modified tri (meth) acrylate phosphate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, and urethane (meth) acrylate.
These acrylic resins may be used alone or in combination of two or more.
6 (3) When it is desired to improve the coating property of the surfactant thermosetting composition, a surfactant can be added in accordance with the purpose. Specific examples of the surfactant added to the thermosetting composition of the present invention include trade names “Byk-300”, “Byk-306”, “Byk-335”, “Byk-310”, “Byk-”. Silicone surfactants such as “341”, “Byk-344”, “Byk-370” (manufactured by Big Chemie); trade names “Byk-354”, “ByK-358”, “Byk-361” Acrylic surfactants (such as those manufactured by Big Chemie Co., Ltd.), and fluorine-based surfactants such as trade names “DFX-18”, “Factent 250”, and “Factent 251” (manufactured by Neos) Can be mentioned.
These surfactants may be used alone or in combination of two or more.
The surfactant is used to improve wettability, leveling property, or coating property to the base substrate, and is used by adding 0.01 to 1 part by weight to 100 parts by weight of the thermosetting composition. It is preferred that

6 (4) Antistatic Agent The antistatic agent added to the thermosetting composition of the present invention is not particularly limited, and a known antistatic agent can be used. Specific examples include metal oxides such as tin oxide, tin oxide / antimony oxide composite oxide, and tin oxide / indium oxide composite oxide, and quaternary ammonium salts.
These antistatic agents may be used alone or in combination of two or more.
The antistatic agent is used to prevent electrification, and is preferably used by adding 0.01 to 1 part by weight to 100 parts by weight of the thermosetting composition.

6 (5) Coupling agent The coupling agent added to the thermosetting composition of the present invention is not particularly limited, and a known coupling agent can be used. The coupling agent to be added is preferably a silane coupling agent, and specific examples thereof include trialkoxysilane compounds and dialkoxysilane compounds. Preferably, for example, γ-vinylpropyltrimethoxysilane, γ-vinylpropyltriethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-acryloylpropyl Triethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycyl Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropylmethyl Rudimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-γ-iminopropylmethyldimethoxysilane, N-aminoethyl-γ-aminopropyl Trimethoxysilane, N-aminoethyl-γ-aminopropyltodiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropylmethyl Dimethoxysilane, N-phenyl-γ-aminopropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopro Le triethoxysilane, .gamma. isocyanate propyl methyl diethoxy silane, .gamma. isocyanate propyl triethoxysilane and the like. Among these, γ-vinylpropyltrimethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like can be given.

These coupling agents may be used alone or in combination of two or more.
The coupling agent is preferably used by adding 0.01 to 3 parts by weight to 100 parts by weight of the thermosetting composition.

6 (6) Epoxy Curing Agent The epoxy curing agent added to the thermosetting composition of the present invention is not particularly limited, and a known epoxy curing agent can be used. Specific examples include organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines, polyvalent carboxylic acids, and polyvalent carboxylic acid anhydrides. More specifically, dicyandiamides such as dicyandiamide, adipic acid dihydrazide, organic acid dihydrazides such as 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 2,4-diamino-6- [2′- Ethylimidazolyl- (1 ′)]-ethyltriazine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, imidazole derivatives such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, phthalic anhydride, Examples include merit acid and acid anhydrides such as 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride.
Of these, trimellitic acid and 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride having good transparency are preferable.

These epoxy curing agents may be used alone or in combination of two or more.
The epoxy curing agent is preferably used by adding 0.2 to 5 parts by weight to 100 parts by weight of the thermosetting composition.

6 (7) Aminosilicon compound An aminosilicon compound can be added to the thermosetting composition of the present invention. Examples of the aminosilicon compound include paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and the like.
These aminosilicon compounds may be used alone or in combination of two or more.
The aminosilicon compound is used to improve the adhesion to the substrate, and is preferably used by adding 0.05 to 2 parts by weight to 100 parts by weight of the thermosetting composition.

7 Viscosity of Thermosetting Composition In the present invention, the viscosity of the thermosetting composition is 51 to 50000 mPa · s (25 ° C.) in that when dispensing is performed at room temperature, the accuracy by the application method using a dispenser is improved. Yes, preferably 100 to 10000 mPa · s (25 ° C.), more preferably 400 to 4000 mPa · s (25 ° C.). When the viscosity exceeds 50000 mPa · s (25 ° C), the viscosity is high, the pressure to be applied is high, and it is difficult to discharge from the needle tip of the dispenser, and the viscosity is less than 51 mPa · s (25 ° C) In such a case, the thermosetting composition has a low viscosity, spreads on the coated substrate, and is not practical.
In the present invention, in order to adjust the viscosity to 51 to 50000 mPa · s (25 ° C.), the silicon amide acid (A), the silicon amide acid (A ′), the polymer compound (B) in the thermosetting composition, and It is obtained by adjusting the solid content concentration of the alkenyl-substituted nadiimide compound (C) and the amount of the solvent (D).

8 Polyimide film The thermosetting composition of the present invention is applied to the substrate surface with a dispenser, and heat-treated with a hot plate or oven to form a polyimide film on the entire surface or in a predetermined pattern (line shape, etc.). Can do. The formation of the polyimide film of the present invention is not limited to heat treatment, and may be treatment with UV treatment, ion beam, electron beam, gamma ray or the like.
Conventionally, a photolithographic technique is used to form a patterned polyimide film, but a large amount of chemicals such as a photoresist, a developer, an etching solution, and a stripping solution are required, and a complicated process is required. It was a thing. On the other hand, the patterned polyimide film formed using the thermosetting composition of the present invention draws only on the necessary part by printing with a dispenser, so the amount of material used is overwhelmingly small, and a photomask is used. Therefore, it is possible to mass-produce a variety of products and to reduce the number of processes required for manufacturing.

8.1 Application of Thermosetting Composition by Dispenser Application Method A preferable discharge method for applying the thermosetting composition according to the present invention is to apply a certain pressure to the syringe and a certain amount of heat from the needle tip. A curable composition is discharged. This can be controlled by a plotter that can be operated freely in the XY directions, and a pattern of a desired thermosetting composition can be drawn. Also, the insulating film pattern can be obtained by a printing method, and examples thereof include screen printing, flexographic printing, offset printing, and gravure printing.

  In addition, when the desired insulating film pattern is a whole surface coating pattern, it can also be applied by a spinner method, a dipping method, or a dropping method.

8.2 Solvent Drying After applying the thermosetting composition of the present invention on the substrate using the dispenser coating method described above, the solvent (D) is heated by using, for example, a hot plate or an oven. The film of silicon amic acid (A) and / or (A ′) can be formed by evaporating and removing it, that is, drying. When the thermosetting composition further contains the polymer compound (B) and the alkenyl-substituted nadiimide compound (C), the silicon amide acid (A) and / or (A ′), the polymer compound (B) and the alkenyl-substituted compound A film of nadiimide compound (C) can be formed.
Although the heating conditions vary depending on the type and blending ratio of each component, a temperature at which the silicon amic acid (A) and (A ′) is not cured is preferable, usually 70 to 120 ° C., and 5 to 60 minutes when using an oven. When a hot plate is used, a dry film is formed in 1 to 30 minutes.

8.3 Formation of polyimide film Silicon amide acid (A) and / or (A ') film, or silicon amide acid (A) and / or (A'), polymer compound (B) and alkenyl substituted nadiimide compound After forming the film of (C), it is preferably 150 to 350 ° C., more preferably 200 to 300 ° C. for imidation of silicon amic acid (A) and / or (A ′) and curing of the silicon part. The polyimide film can be obtained by heat treatment (30 to 120 minutes when using an oven, 5 to 60 minutes when using a hot plate). In addition, when the high molecular compound (B) is a polyamic acid, a polyamic acid ester, or the like, an imidization reaction by heat treatment also proceeds simultaneously.
When the film is formed in a pattern, a patterned polyimide film is formed. In this specification, unless otherwise specified, the polyimide film includes a patterned polyimide film.

  The polyimide film thus obtained is an insulating film excellent in heat resistance, electrical insulation and low warpage. Moreover, when the raw material thermosetting composition contains an epoxy resin, it is preferable because it is relatively strong and becomes an insulating film excellent in chemical resistance, flatness, adhesion, and sputtering resistance.

9 Film substrate The film substrate of the present invention is, for example, on the entire surface or a predetermined pattern (line shape, etc.) by applying the thermosetting composition of the present invention on a substrate such as a polyimide film on which wiring has been formed in advance by a dispenser. Then, the substrate is dried and further heated to obtain an electronic component such as a flexible film substrate partially or entirely covered with an insulating polyimide film.

10 Silicon wafer substrate For example, by applying the thermosetting composition of the present invention on a silicon wafer substrate on which wiring is formed in advance by a dispenser coating method, and then drying and further heating the silicon wafer substrate. In addition, an electronic component such as a semiconductor coated with an insulating polyimide film can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to these Examples.

  Compound (a1) having two or more acid anhydride groups, monoamine (a2), compound (a1 ′) having one acid anhydride group, diamine (a2 ′), acid anhydride used in Examples and Comparative Examples The names of the compound (b1), diamine (b2), monoamine (b3), alkenyl-substituted nadiimide (C), and solvent (D) having two or more groups are abbreviated. This abbreviation is used in the following description.

Compounds (a1) and (b1) having two or more acid anhydride groups
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 6FDA: 4,4′-hexafluoropropylidenebis Phthalic dianhydride

Monoamine (a2), (b3)
APSE: 3-aminopropyltriethoxysilane

Compound having one acid anhydride group (a1 ′)
TESA: Triethoxysilylpropyl succinic anhydride

Diamine (a2 ′), (b2)
DDS: 3,3′-diaminodiphenylsulfone PDA: p-phenylenediamine 7HHP: 5-[((n-heptylcyclohexyl) ethylcyclohexyl) phenyl] methyl-1,3-diaminobenzene 7HB: 1,1-bis [4 -(4-Aminobenzyl) phenyl] -4-n-heptylcyclohexane BAP: 2,2-bis [4- (4-amino-2-methylphenoxy) phenyl] propane

Alkenyl-substituted nadiimide (C)
BANIM: bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane

Solvent (D)
EDM: Diethylene glycol methyl ethyl ether GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone

[Example 1] Thermosetting composition (1)
A 200 ml three-necked flask equipped with a stirrer and a raw material charging inlet was charged with raw materials as shown below and stirred for 3 hours at room temperature in a dry nitrogen stream. A transparent silicon amic acid (A) 60% by weight solution Got. The obtained solution was a thermosetting composition (1), and this solution was used as the thermosetting composition.
The viscosity of this solution was 510 mPa · s (25 ° C.). The viscosity of the solution was measured with an E-type viscometer (VISCONIC EHD manufactured by TOKYO KEIKI).
a1: ODPA 12.4g
a2: APSE 17.6g
D: 10.0 g EDM
D: GBL 10.0g

[Example 2] Thermosetting composition (2)
When a raw material was charged as shown below into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, the mixture was stirred for 5 hours at 40 ° C. in a dry nitrogen stream. A 60% by weight solution of polyamic acid (B) was obtained.
The viscosity of this solution was 3500 mPa · s. The weight average molecular weight measured by GPC was 2,100. The weight average molecular weight of the polyamic acid is obtained by diluting the obtained polyamic acid with tetrahydrofuran (THF) so that the polyamic acid concentration is about 1% by weight, and as a GPC device, JASCO GULLIVER 1500 (intelligent differential refraction). Using a ratio meter RI-1530), the dilution was measured by the GPC method using a developing agent, and determined by polystyrene conversion. Four columns, Tosoh Corporation columns G4000HXL, G3000HXL, G2500HXL and G2000HXL, were connected in this order and measured under the conditions of a column temperature of 40 ° C. and a flow rate of 1.0 ml / min.
b1: ODPA 55.0g
b2: DDS 11.0g
b3: APSE 59.0 g
D: GBL 83.3g

The silicon amide acid (A) solution of Example 1 and this polyamic acid (B) solution were charged as shown below and stirred for 2 hr to obtain a 60% by weight solid content solution. This solution was used as a thermosetting composition (2). The viscosity of this solution was 1280 mPa · s (25 ° C.).
Silicon amic acid (A) solution 64.0 g
Polyamic acid (B) solution 32.0 g

[Example 3] Thermosetting composition (3)
The silicon amide acid (A) solution of Example 1 and the alkenyl-substituted nadiimide (C) were charged as shown below, and stirred until the solid content was completely dissolved. Silicon amide acid (A) / alkenyl-substituted nadiimide A 60 wt% solution of (C) was obtained. This solution was used as a thermosetting composition (3). The viscosity of this solution was 400 mPa · s (25 ° C.).
Silicon amic acid (A) solution 50g
C: BANIM 15g
D: GBL 5g
D: EDM 5g

[Example 4]
The thermosetting composition (1) prepared in Example 1 was sealed in a dispenser injection container, and a needle tip width of 1 mm was attached. Pressurization was performed at 1 kgf / cm ² using a dispenser coating apparatus ML505X manufactured by MUSASHI Engineering, and a line having a length of 5 cm was applied onto a silicon wafer at 10 mm / sec using SHOTMASTER 3. The substrate was dried on an 80 ° C. hot plate for 10 minutes, and then heated in an oven at 230 ° C. for 30 minutes to obtain a polyimide insulating film formed in a line shape.
The line width of the obtained polyimide film and the uniformity of the line width were observed with an optical microscope, and the film thickness was measured. For the film thickness, a stylus type film thickness meter α step 200 manufactured by KLA-Tencor Japan Co., Ltd. was used, and the average value of three measured values was defined as the film thickness. The results are shown in Table 1. The line had a sufficient thickness.

[Example 5]
Using the thermosetting composition (2) prepared in Example 2, a polyimide insulating film was obtained under the same conditions as in Example 4.
The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The line had a sufficient thickness.

[Example 6]
Using the thermosetting composition (3) prepared in Example 3, a polyimide insulating film was obtained under the same conditions as in Example 4.
The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The line had a sufficient thickness.

[Comparative Example 1] Thermosetting composition (4)
Polyamic acid was charged as shown below under the same conditions as in Example 1 and stirred at room temperature under a dry nitrogen stream to obtain a 12 wt% solution of the polymer compound (B). This solution was used as a thermosetting composition (4). The viscosity of this solution was 3100 mPa · s.
ODPA 15.5g
BAP 20.5g
D: EDM 132.0g
D: GBL 132.0g

[Comparative Example 2]
A polyimide insulating film was obtained under the same conditions as in Example 4 except that the thermosetting composition (4) prepared in Comparative Example 1 was used.
The obtained polyimide film was evaluated under the same conditions as in Example 4. The results are shown in Table 1. The line did not have a thickness exceeding 100 μm.

Example 7 Preparation of Thermosetting Composition (5) and Formation of Polyimide Insulating Film A thermosetting composition was prepared by the same method as in Example 1 except that the raw materials were charged as shown below. It was measured.
a1: BTDA 12.6g
a2: APSE 17.4g
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

[Example 8] Preparation of thermosetting composition (6) and formation of polyimide insulating film A thermosetting composition was prepared by the same method as in Example 1 except that the raw materials were charged as shown below. It was measured.
a1: 6FDA 15.0g
a2: APSE 15.0g
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

[Example 9] Preparation of thermosetting composition (7) and formation of polyimide insulating film A thermosetting composition was prepared by the same method as in Example 1 except that the raw materials were charged as shown below. It was measured.
a1 ′: 21.3 g of TESA
a2 ': DDS 8.7g
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

[Example 10] Preparation of thermosetting composition (8) and formation of polyimide insulating film A thermosetting composition was prepared by the same method as in Example 1 except that the raw materials were charged as shown below. It was measured.
a1 ': 25.5 g of TESA
a2 ': PDA 4.5g
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

[Example 11] Preparation of thermosetting composition (9) and formation of polyimide insulating film A thermosetting composition was prepared by the method according to Example 1 except that the raw materials were charged as shown below, and the viscosity was adjusted. It was measured.
a1 ′: TESA 16.6 g
a2 ′: 13.4 g of 7HHP
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

[Example 12] Preparation of thermosetting composition (10) and formation of polyimide insulating film A thermosetting composition was prepared by the same method as in Example 1 except that the raw materials were charged as shown below. It was measured.
a1 ′: 15.8 g of TESA
a2 ′: 7.HB 14.2 g
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

[Example 13] Preparation of thermosetting composition (11) and formation of polyimide insulating film A thermosetting composition was prepared by the same method as in Example 1 except that the raw materials were charged as shown below. It was measured.
a1 ′: TESA 17.9 g
a2 ′: BAP 12.1 g
D: 10.0 g EDM
D: GBL 10.0g
Further, a polyimide insulating film was formed by a method according to Example 4.

  About Example 7-Example 12, about the obtained polyimide film, it evaluated on the same conditions as Example 4. FIG. The results are shown in Table 2. The line had a sufficient thickness.

  Examples of the utilization method of the present invention include an insulating film for a flexible wiring board, an insulating film such as a semiconductor, and an electronic component using the same.

Claims (24)

Silicon compound (A) obtained using compound (a1) having two or more acid anhydride groups and monoamine (a2), and compound (a1 ′) and diamine (a2 ′) having one acid anhydride group And at least one selected from silicon compounds (A ′) obtained by using a polymer compound (B),
The silicon compound (A) is a silicon amide acid (A) represented by the general formula (3), and the silicon compound (A ′) is a silicon amide acid (A ′) represented by the general formula (3 ′). The polymer compound (B) has a weight average molecular weight of 1,000 to 50,000, at least a compound (b1) having two or more acid anhydride groups, a diamine (b2), and a monoamine (b3) And at least one selected from polyamic acid and polyimide obtained using
The compounds (a1) and (b1) having two or more acid anhydride groups may be the same or different and are tetracarboxylic dianhydrides represented by the general formula (1), and are monoamine (a2 ) And (b3) may be the same or different and are aminosilicon compounds represented by the general formula (2),
The compound (a1 ′) having one acid anhydride group is a dicarboxylic acid anhydride represented by the general formula (1 ′), and the diamines (a2 ′) and (b2) are the same or different. May be a diamine represented by the general formula (2 ′),
A thermosetting composition having a viscosity of 51 to 50000 mPa · s (25 ° C.).

(In General Formula (1), X is a tetravalent organic group having 2 to 100 carbon atoms. In General Formula (2), R ¹ , R ² and R ³ are independently hydrogen, halogen or monovalent. These may be the same or different, and Y is a divalent organic group having 1 to 20 carbon atoms.)

(In the general formula (1 ′), R ¹ , R ² and R ³ are independently hydrogen, halogen or a monovalent organic group, and they may be the same or different, and Y ′ represents the number of carbon atoms. 1 to 20 trivalent organic groups, and in the general formula (2 ′), X ′ is a divalent organic group having 2 to 100 carbon atoms.

(In General Formula (3), X is a tetravalent organic group having 2 to 100 carbon atoms, R ¹ , R ² and R ³ are independently hydrogen, halogen or a monovalent organic group, They may be the same or different, and Y is a divalent organic group having 1 to 20 carbon atoms.)

(In General Formula (3 ′), R ¹ , R ^2, and R ³ are independently hydrogen, halogen, or a monovalent organic group, and they may be the same or different, and Y ′ is the number of carbon atoms. 1 to 20 trivalent organic groups, and X ′ is a divalent organic group having 2 to 100 carbon atoms.) The tetracarboxylic dianhydride is pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl Sulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane Anhydride, ethylene glycol bis (anhydrotrimellitate), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetra One or more selected from the group consisting of carboxylic dianhydride, ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride,
The aminosilicon compound is selected from the group consisting of paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, aminopropyltrimethoxysilane, and aminopropyltriethoxysilane. One or more,
The thermosetting composition according to claim 1 . The thermosetting composition according to claim 1, wherein the silicon amide acid (A) is a silicon amide acid represented by the general formula (4-1), (4-2) or (4-3).

(Formula (4-1), (4-2) and (4-3), R ^1, R ² and R ³ are independently hydrogen, halogen or a monovalent organic group, R ^1, At least one of R ² and R ³ includes alkoxy having 1 to 20 carbons, and a is an integer of 1 to 20) The ratio of the compound (a1) having two or more acid anhydride groups and the monoamine (a2) is 1 mol: 0.5 to 8.0 mol, according to any one of claims 1 to 3 . Thermosetting composition. The dicarboxylic acid anhydride of the general formula (1 ′) is p- (trimethoxysilyl) phenyl succinic anhydride, p- (triethoxysilyl) phenyl succinic anhydride, m- (trimethoxysilyl) phenyl succinic. One or more selected from the group consisting of an anhydride, m- (triethoxysilyl) phenyl succinic anhydride, trimethoxysilylpropyl succinic anhydride, and triethoxysilylpropyl succinic anhydride,
The diamine of the general formula (2 ′) is p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-1,2-diphenylethane, 4, 4'-diamino-1,3-diphenylpropane, 2,2-bis (4-aminophenyl) propane, bis (4-amino-3-methylphenyl) methane, 1,2-bis- (4-amino-3) -Methylphenyl) ethane, bis (4-amino-2-methylphenyl) methane, 1,2-bis- (4-amino-2-methylphenyl) ethane, 4,4'-diaminodiphenyl ether, 3,3'- diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4, '-Diaminobenzophenone, 4,4'-diaminodiphenyl-2,2'-propane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,4-bis [(4-aminophenyl) methyl] Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] fluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] biphenyl, 1,3-bis [4 -(4-aminobenzyl) phenyl] propane, 1,6-bis [4- (4-aminobenzyl) phenyl] hexane, 5-pheny Methyl-1,3-diaminobenzene, 5- [4- (4-alkylcyclohexyl) phenyl] methyl-1,3-diaminobenzene, 5- [4- (4- (4-alkylcyclohexyl) cyclohexyl) phenyl] methyl -1,3-diaminobenzene, 5-[((alkylcyclohexyl) ethylcyclohexyl) phenyl] methyl-1,3-diaminobenzene, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1, 1-bis [4- (4-aminophenoxy) phenyl] -4-alkylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-amino) Benzyl) phenyl] -4-alkylcyclohexane, 1,3-bis (3-aminopropyl) -tetramethyl At least one selected from the group consisting distearate siloxane claim 1 thermosetting composition. The silicon amic acid (A ′) is represented by the general formula (4′-1), (4′-2), (4′-3), (4′-4) or (4′-5). The thermosetting composition according to claim 1, which is silicon amic acid (A ′).

(In the general formulas (4'-1), (4'-2), (4'-3), (4'-4) and (4'-5), R ¹ , R ² and R ³ are independently Hydrogen, halogen or a monovalent organic group, which may be the same or different, and at least one of R ¹ , R ² and R ³ contains an alkoxy having 1 to 20 carbon atoms; a is an integer of 1 to 19, R in the general formula (4′-3) is an organic group having 2 to 30 carbon atoms, and R in the general formula (4′-4) is hydrogen or 1 to 19 carbon atoms. 20 alkyls.) The ratio of the compound (a1 ′) having one acid anhydride group and the diamine (a2 ′) is 0.5 to 8.0 mol: 1 mol, according to any one of claims 1 to 6. Thermosetting composition. Further includes alkenyl substituted nadimide (C), the thermosetting composition according to any one of claims 1-7. The thermosetting composition according to claim 8 , wherein the alkenyl-substituted nadiimide (C) is a compound represented by the general formula (5).

(In General Formula (5), R ¹ and R ² 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. Any one of aryl and benzyl, n is an integer of 1 to 2,
When n = 1, R ³ 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, s is an integer of from 2 to 6 selected independently, t is an integer of 0 or 1 And u is an integer of 1 to 30, X is hydrogen or a hydroxyl group, and-(R) _a -C ₆ H ₄ -R ⁴ (where a is an integer of 0 or 1) , R is alkylene having 1 to 4 carbon atoms, R ⁴ is 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 - is a In a group represented by or a group 1 to 3 hydrogens directly bonded to the aromatic ring is replaced with a hydroxyl group of these groups,
When n = 2, R ³ is alkylene represented by —C _p H _2p — (where 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 and u is 1 to 30 integer Is a polyoxyalkylene, an arylene having 6 to 12 carbon atoms,-(R) _a -C ₆ H ₄ -R ^5- (where a is an integer of 0 or 1, R and R ⁵ are groups represented by independently is selected alkylene having 1 to 4 carbon _{atoms), -C 6 H 4 -T-} C 6 H 4 - ( where, T is _{-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 - in a is) Or a group in which 1 to 3 hydrogen atoms directly bonded to the aromatic ring of these groups are replaced with a hydroxyl group. ) The thermosetting composition according to claim 9 , wherein n is 2 in the general formula (5). n is 2,
In the general formula (5), R ³ is alkylene represented by —C _p H _2p — (where p is an integer of 2 to 10), — (R) _a —C ₆ H ₄ —R ⁵ — Wherein a is an integer of 0 or 1, R and R ⁵ are independently selected alkylene having 1 to 4 carbon atoms, or —C ₆ H ₄ —TC ₆ H ₄ - (where, T is _{-CH 2 -, - C (CH} 3) 2 -, - CO -, - O -, - OC 6 H 4 C (CH 3) 2 C 6 H 4 O -, - S The thermosetting composition according to claim 9 , which is a group represented by — or —SO ₂ —. In the general formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms,
n is 2,
The thermosetting composition according to claim 9 , wherein R ³ is — (CH ₂ ) ₆ —, a group represented by formula (6), or a group represented by formula (7).

In the above general formula (5), n comprises at least one alkenyl-substituted nadimide compound (C) is 1, the alkenyl substituted nadiimide compounds wherein n is 2 and at least one (C), according to claim 9, wherein Thermosetting composition. In the general formula (5), n is 1, R ³ is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons, benzyl,-{(C _q H in _{2q) O t (C r H} 2r O) u C s H 2s + 1} ( where, q, r, s is an integer of from 2 to 6 selected independently, t is an integer of 0 or 1 and u is 1 -(R) _a -C ₆ H ₄ -R ⁴ (where a is an integer of 0 or 1 and R is an alkylene having 1 to 4 carbon atoms) , R ⁴ represents hydrogen or a group having 1 to 4 carbon atoms, or —C ₆ H ₄ —TC ₆ H ₅ (where T is —CH ₂ —, —C ( _{CH 3) 2 -, - CO} -, - S- or SO ₂ - is a group represented by a is) Al And at least one alkenyl-substituted nadimide compound (C),
The thermosetting composition of Claim 9 containing at least 1 sort (s) of the alkenyl substituted nadiimide compound (C) whose n is 2. In the general formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 1, R ³ is alkyl having 1 to 12 carbon atoms, and 5 to 5 carbon atoms. At least one alkenyl-substituted nadiimide compound (C) that is 8 cycloalkyl, aryl having 6 to 12 carbon atoms, or benzyl;
The thermosetting composition of Claim 9 containing at least 1 sort (s) of the alkenyl substituted nadiimide compound (C) whose n is 2. In the general formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 1, and R ³ is alkyl having 1 to 12 carbon atoms or 6 to 6 carbon atoms. At least one alkenyl-substituted nadiimide compound (C) that is 12 aryls;
R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, R ³ is — (CH ₂ ) ₆ —, a group represented by the formula (6): The thermosetting composition of Claim 9 containing at least 1 sort (s) of the alkenyl substituted nadiimide compound (C) which is group represented by 7).

Further comprising a solvent (D), the thermosetting composition according to any of claims 1-16. Solvent (D) 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 The thermosetting composition according to claim 17 , which is one or more selected from the group consisting of glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone and γ-butyrolactone. A polyimide film or a patterned polyimide film obtained by applying the thermosetting composition according to any one of claims 1 to 18 by a dispenser coating method to form a coating film, and then curing the coating film. A polyimide comprising a step of applying the thermosetting composition according to any one of claims 1 to 18 by a dispenser coating method to form a coating film, and a step of curing the coating film to form a polyimide film. A method for forming a film or a patterned polyimide film. A film substrate having a polyimide film or a patterned polyimide film formed on the substrate by the method according to claim 20 . An electronic component comprising the film substrate according to claim 21 . A silicon wafer substrate having a polyimide film or a patterned polyimide film formed on the substrate by the method according to claim 20 . An electronic component having the silicon wafer substrate according to claim 23 .