JP5540483B2 - Thermosetting composition, method for producing the composition, and use of the composition - Google Patents

Description

  The present invention relates to a thermosetting composition, for example, a thermosetting composition containing an alkenyl-substituted nadiimide and a polyamic acid, which can be used in forming an insulating film layer in the manufacture of electronic components, and the thermosetting composition And a polyimide film obtained from the thermosetting composition, a method for producing the polyimide film, a film substrate having the polyimide film, a silicon wafer substrate, and an electronic component having the film substrate or the silicon wafer substrate.

  Polyimide is a thermosetting material widely used in the field of electronic communication because it is excellent in 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 by a photolithographic technique using photosensitive polyimide.

  However, when forming a pattern using the photolithographic technique, a large amount of chemicals such as a photoresist, a developing solution, an etching solution, and a stripping solution are required, and a complicated process is required. Therefore, as a method capable of forming a pattern only in a necessary portion by a simple process, not by photolithography, a desired method is obtained by applying a thermosetting composition by screen printing, inkjet printing or a dispenser. A method of forming a patterned coating film and curing the coating film to obtain a patterned film has been studied.

  Usually, as a thermosetting composition which becomes a polyimide when cured, a composition containing polyamic acid as a polyimide precursor or a composition in a solution state containing a solvent-soluble polyimide is used. The solid content of the polyamic acid or soluble polyimide is usually high in molecular weight, and in order to prepare a composition containing the solid content of polyamic acid or soluble polyimide to an optimum viscosity as a thermosetting composition for a dispenser, It is necessary to increase the ratio to reduce the solid content concentration in the composition. However, the pattern film formed using a thermosetting composition having a large proportion of the solvent volatilizes the solvent in the thermosetting composition before obtaining the pattern film. There is a problem that the film thickness of the pattern film is significantly smaller than that of the object, and the film thickness of the pattern film does not become a desired thickness. In addition, when a patterned coating film is cured to obtain a pattern film, there is a problem that the film tends to undergo curing shrinkage and the substrate warps.

Therefore, a polyamide-imide resin having flexibility has been proposed as a thermosetting composition having low warpage. However, the polyamide-imide resin is usually insufficient in heat resistance and electrical insulation as compared with the polyimide resin.
JP 2000-039714 A JP 2003-238683 A JP 2004-094118 A

  The present invention has been made in view of the above-described problems of the prior art, and can be used in various coating methods such as a dispenser coating method without lowering the concentration of solid components in the composition. It is an object of the present invention to provide a thermosetting composition having electrical insulation properties, low warpage, and capable of forming a relatively thick polyimide film (100 μm or more).

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found a thermosetting composition containing an alkenyl-substituted nadiimide (C) and a specific polyamic acid (B).
That is, the present invention relates to [1] to [27].
[1] Alkenyl substituted nadiimide (C),
And a thermosetting composition comprising a polyamic acid (B) having a structural unit represented by the following formula (2) and having a weight average molecular weight of 25,000 to 50,000.

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.)
[2] Polyamic acid in which the polyamic acid (B) has at least one molecular end group selected from the group consisting of a group represented by the following formula (21) and a group represented by the following formula (22) The thermosetting composition according to [1].

(In formula (21), R ⁵ is an organic group having 2 to 100 carbon atoms, and in formula (22), R ⁶ is an organic group having 2 to 100 carbon atoms.)
[3] The polyamic acid (B) is at least one monomer selected from the group consisting of a compound represented by the following formula (13) and a compound represented by the following formula (14), the following formula (11) The thermosetting composition according to [1], which is a polyamic acid obtained by copolymerizing a compound represented by formula (I) and a compound represented by the following formula (12).

(In the formula (11), R ³ is an organic group having 2 to 100 carbon atoms, in the formula (12), R ⁴ is an organic group having 2 to 100 carbon atoms, and in the formula (13), R ⁶ is an organic group of 2 to 100 carbon atoms, in the formula (14), R ⁵ is an organic group having 2-100 carbon atoms.)
[4] Alkenyl substituted nadiimide (C),
And a thermosetting composition comprising a polyamic acid (B) having a structural unit represented by the following formula (2):
The polyamic acid (B) is at least one molecular end selected from the group consisting of a group represented by the following formula (23), a group represented by the following formula (24), and a group represented by the following formula (25) A thermosetting composition which is a polyamic acid having a group.

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.)
[5] Alkenyl substituted nadiimide (C),
And a thermosetting composition comprising a polyamic acid (B) having a structural unit represented by the following formula (2):
The polyamic acid (B) is at least one compound selected from the group consisting of maleic anhydride and citraconic anhydride, a compound represented by the following formula (11), and a compound represented by the following formula (12) A thermosetting composition which is a polyamic acid obtained by copolymerization of

(In Formula (2) and Formula (11), R ³ is an organic group having 2 to 100 carbon atoms, and in Formula (2) and Formula (12), R ⁴ is an organic group having 2 to 100 carbon atoms. .)
[6] The thermosetting composition according to any one of [1] to [5], wherein the alkenyl-substituted nadiimide (C) is a compound represented by the following formula (5).

(In formula (5), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, 6 to 12 carbon atoms Either aryl or benzyl, n is 1 or 2,
When n = 1, Q is hydrogen, hydroxyl group, alkyl having 1 to 12 carbon atoms, alkenyl having 1 to 3 carbon atoms, hydroxyalkyl having 1 to 12 carbon atoms, hydroxyalkenyl having 2 to 12 carbon atoms, or 5 to 5 carbon atoms. Cycloalkyl having 8 carbon atoms, hydroxycycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, — [(C _q H _2q ) O _t (C _r H _2r O) _u C _s H _2s X] A group represented by the formula (wherein q, r, and s are each independently an integer of 2 to 6, t is 0 or 1, u is an integer of 0 to 30, and X is hydrogen or a hydroxyl group),-( R) _a group represented by _a- C ₆ H ₄ -R ⁴¹ (where a is 0 or 1, R is alkylene having 1 to 4 carbon atoms, R ⁴¹ is hydrogen or alkyl having 1 to 4 carbon atoms) _{), - C 6 H 4 -T} -C 6 H 5 , a group represented by the table in _{-C 6 H 4 -T-C 6} H 4 -OH Group (wherein, T is _{-CH 2 -, - C (CH} 3) 2 -, isopropylidene, -CO -, - S- or -SO ₂ - in which), or their groups containing an aromatic ring In the case, 1 to 3 hydrogen atoms directly bonded to the aromatic ring are groups substituted with a hydroxyl group,
When n = 2, Q is alkylene having 2 to 20 carbons, cycloalkylene having 5 to 8 carbons,-[(C _q H _2q O) _t (C _r H _2r O) _u C _s H _2s ]- A group represented by the formula (wherein q, r and s are each independently an integer of 2 to 6, t is 0 or 1, u is an integer of 1 to 30), an arylene having 6 to 12 carbon atoms,-( R) _a group represented by _a —C ₆ H ₄ —R ⁵¹ — (wherein, a is 0 or 1, R and R ⁵¹ each independently represent alkylene having 1 to 8 carbons, or cyclohexane having 1 to 8 carbons) A group represented by —C ₆ H ₄ —TC ₆ H ₄ — (wherein T represents —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—). , —OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ O—, —S—, —SO ₂ —), or when these groups contain an aromatic ring, 3 hydrogens Is a group that has been replaced by a hydroxyl group. )
[7] The thermosetting composition according to [6], wherein n is 2 in the formula (5).
[8] In the formula (5), n is 2, Q is alkylene having 2 to 10 carbon atoms, a group represented by — (R) _a —C ₆ H ₄ —R ⁵¹ — (where a Is 0 or 1, R and R ⁵¹ are each independently alkylene having 1 to 4 carbon atoms, or a group represented by —C ₆ H ₄ —T—C ₆ H ₄ — (wherein T is — CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ O—, —S—, —SO ₂ —) The thermosetting composition according to [6].
[9] In the above formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, Q is — (CH ₂ ) ₆ —, formula (6) The thermosetting composition according to [6], which is a group represented by formula (7) or a group represented by formula (7):

[10] The alkenyl-substituted nadiimide compound (C) includes at least one compound in which n is 1 in the formula (5) and at least one compound in which n is 2 in the formula (5) [ 6].
[11] An alkenyl-substituted nadiimide compound (C), wherein n is 1 in the formula (5), Q is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, and 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] , a group represented by (wherein, q, r, s independently of 2-6 An integer, t is 0 or 1, u is an integer of 1 to 30, and a group represented by — (R) _a —C ₆ H ₄ —R ⁴¹ (where a is 0 or 1, and R is carbon. An alkylene having 1 to 4; R ⁴¹ represents hydrogen or alkyl having 1 to 4 carbons; or a group represented by —C ₆ H ₄ —TC ₆ H ₅ (wherein T is —CH _{2 -, - C (CH 3)} 2 -, - CO -, - at least one compound is a is), - S- or -SO ₂
The thermosetting composition according to [6], including at least one compound in which n is 2 in the formula (5).
[12] In the alkenyl-substituted nadiimide compound (C), in formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 1, and Q is 1 carbon. At least one compound which is ˜12 alkyl, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, or benzyl;
The thermosetting composition according to [6], including at least one compound in which n is 2 in the formula (5).
[13] In the alkenyl-substituted nadiimide compound (C), in formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 1, and Q is 1 carbon. At least one compound which is ˜12 alkyl or C 6-12 aryl;
In the formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, Q is represented by-(CH ₂ ) _6- , and the formula (6). Or at least one compound which is a group represented by the formula (7).

[14] The thermosetting composition according to any one of [1] to [13], further including a solvent (D). [15] 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 Thermosetting according to [14], which is at least one solvent selected from the group consisting of acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone and γ-butyrolactone Composition.
[16] A polyimide film obtained by applying the thermosetting composition according to any one of [1] to [15] on a substrate to form a coating film, and then curing the coating film.
[17] The polyimide film as described in [16], wherein the coating is performed by a dispenser coating method.
[18] The polyimide film as described in [16] or [17], wherein the polyimide film is a patterned polyimide film.
[19] A step of applying the thermosetting composition described in any one of [1] to [15] onto a substrate to form a coating film, and curing the coating film to form a polyimide film. The manufacturing method of the polyimide film containing a process.
[20] The method for producing a polyimide film as described in [19], wherein the coating is performed by a dispenser coating method.
[21] The method for producing a polyimide film according to [19] or [20], wherein the polyimide film is a patterned polyimide film.
[22] A film substrate having the polyimide film according to any one of [16] to [18].
[23] An electronic component having the film substrate according to [22].
[24] A silicon wafer substrate having the polyimide film according to any one of [16] to [18].
[25] An electronic component having the silicon wafer substrate described in [24].
[26] at least one monomer selected from the group consisting of a compound represented by the following formula (13) and a compound represented by the following formula (14) in the presence of an alkenyl-substituted nadiimide (C) and a solvent (D); Copolymerizing a compound represented by the following formula (11) and a compound represented by the following formula (12);
It has a structural unit represented by alkenyl-substituted nadiimide (C) and the following formula (2), has a weight average molecular weight of 25,000 to 50,000, a group represented by the following formula (21) and the following formula (22 The method of manufacturing the thermosetting composition containing the polyamic acid (B) which has at least 1 sort (s) of molecular end groups selected from the group which consists of group represented by this.

(In the formulas (2) and (11), R ³ is an organic group having 2 to 100 carbon atoms. In the formulas (2) and (12), R ⁴ is an organic group having 2 to 100 carbon atoms. In (13) and (22),
R ⁶ is an organic group having 2 to 100 carbon atoms, and in formulas (14) and (21), R ⁵ is an organic group having 2 to 100 carbon atoms. )
[27] At least one compound selected from the group consisting of maleic anhydride and citraconic anhydride in the presence of alkenyl-substituted nadiimide (C) and solvent (D), a compound represented by the following formula (11), and the following formula Copolymerizing the compound represented by (12),
An alkenyl-substituted nadiimide (C) and a structural unit represented by the following formula (2), a group represented by the following formula (23), a group represented by the following formula (24), and a formula (25) A method for producing a thermosetting composition comprising a polyamic acid (B) having at least one molecular end group selected from the group consisting of represented groups.
.

(In formulas (2) and (11), R ³ is an organic group having 2 to 100 carbon atoms, and in formulas (2) and (12), R ⁴ is an organic group having 2 to 100 carbon atoms.)

  When the thermosetting composition of the present invention is used, a polyimide film having a thick film thickness as compared with the conventional curable composition can be formed by one coating and curing treatment. Moreover, the polyimide film formed from the thermosetting composition of the present invention has high heat resistance and electrical insulation, and improves the reliability and yield of electronic components.

  The patterned polyimide film formed by using the thermosetting composition of the present invention can apply the thermosetting composition only to a necessary portion by a dispenser coating method, thus reducing the amount of material used. be able to. In addition, since the dispenser coating method can form a pattern without using a photomask, it can be mass-produced for a variety of products and requires a small number of processes.

The thermosetting composition of the present invention includes an alkenyl-substituted nadiimide (C) and a polyamic acid (B) having a structural unit represented by the following formula (2), and is used as the polyamic acid (B) used in the present invention. Has two aspects.

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.)
The polyamic acid (B1) which is the first embodiment of the polyamic acid (B) has a structural unit of the formula (2) and has a weight average molecular weight of 25,000 to 50,000. The polyamic acid (B2) which is the second embodiment of the polyamic acid (B) is composed of a group represented by the following formula (23), a group represented by the following formula (24), and a group represented by the following formula (25). Having at least one molecular end group selected from the group consisting of

The thermosetting composition of the present invention may be colorless or colored. Moreover, the thermosetting composition of the present invention may further contain a solvent (D).
[1.1 Polyamic acid (B1)]
The polyamic acid (B1) has a structural unit represented by the formula (2) and has a weight average molecular weight of 25,000 to 50,000.

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.)
The polyamic acid (B1) contained in the thermosetting composition of the present invention is preferably at least one selected from the group consisting of a group represented by the following formula (21) and a group represented by the following formula (22). Has molecular end groups.

In said formula, R < ³ > -R < ⁶ > is a C2-C100 organic group each independently.
The polyamic acid (B1) used in the present invention usually has at least one monomer selected from the group consisting of a compound (a1 ′) having one acid anhydride group and a monoamine (a2 ′), and two acid anhydride groups. It is produced by copolymerizing at least one compound (a1) and diamine (a2), but is not limited to the polyamic acid (B1) obtained by the production method, and the polyamic acid (B1) obtained by another production method ) May be used.

[1.2 Weight Average Molecular Weight of Polyamic Acid (B1)]
The polyamic acid (B1) used in the present invention has a weight average molecular weight of 25,000 to 50,000. Within this range, a thermosetting composition that is excellent in solubility in a solvent and can be applied by a dispenser coating method or the like can be obtained. In addition, from the viewpoint of solubility of the polyamic acid (B1) in the solvent, the weight average molecular weight of the polyamic acid (B1) is more preferably 25,000 to 45,000, and 25,000 to 35,000. Is more preferable.

  Since the polyamic acid (B1) has a weight average molecular weight of 25,000 or more, it evaporates even when the coating film formed by applying the thermosetting composition is subjected to a curing treatment by heating. There is no chemical and mechanical stability. Moreover, since the weight average molecular weight of polyamic acid (B1) is 50,000 or less, it is excellent in solubility in a solvent, and the concentration of polyamic acid (B1) dissolved in the solvent can be increased. Therefore, it is possible to increase the film thickness of the polyimide film obtained by applying a curing treatment by heating to the coating film formed by applying the thermosetting composition, which is suitable as a thermosetting composition. is there.

  In addition, the weight average molecular weight of the polyamic acid (B1) used for this invention was measured by the gel permeation chromatography (GPC) method. Specifically, the polyamic acid (B1) is diluted with tetrahydrofuran (THF) or the like to a concentration of about 1% by weight, and THF is used as a developing agent using columns G4000HXL, G3000HXL, G2500HXL and G2000HXL manufactured by Tosoh Corporation. As measured by gel permeation chromatography (GPC) method and calculated by polystyrene conversion.

[1.3 Reaction Conditions for Obtaining Polyamic Acid (B1)]
The polyamic acid (B1) is usually a compound having at least one monomer selected from the group consisting of a compound (a1 ′) having one acid anhydride group and a monoamine (a2 ′), and two or more acid anhydride groups. It can be obtained by copolymerizing (a1) and diamine (a2).

When the polyamic acid (B1) is synthesized by copolymerizing a compound (a1 ′) having one acid anhydride group, a compound (a1) having two or more acid anhydride groups and a diamine (a2) , A compound having two or more acid anhydride groups (a1 per 1 mol of diamine (a2))
) Compound (a1 ′) having 0.6 to 0.999 mol and one acid anhydride group It is preferable to use 0.002 to 0.8 mol, and the acid anhydride group is used with respect to 1 mol of diamine (a2). It is more preferable to use 0.82 to 0.99 mol of the compound (a1) having 2 or more and 0.02 to 0.4 mol of the compound (a1 ′) having one acid anhydride group. In this case, a polyamic acid (B1) having a group represented by the above formula (22) at the molecular end is obtained.

When the polyamic acid (B1) is synthesized by copolymerizing a monoamine (a2 ′), a compound (a1) having two or more acid anhydride groups and a diamine (a2), two acid anhydride groups are present. It is preferable to use 0.6 to 0.999 mol of diamine (a2) and 0.002 to 0.8 mol of monoamine (a2 ′) with respect to 1 mol of the compound (a1) having two or more acid anhydride groups. More preferably, 0.8 to 0.99 mol of diamine (a2) and 0.02 to 0.4 mol of monoamine (a2 ′) are used per 1 mol of compound (a1). In this case, a polyamic acid (B1) having a group represented by the above formula (21) at the molecular end is obtained.

  Polyamide acid (B1) is copolymerized with compound (a1) having two or more acid anhydride groups, compound (a1 ′) having one acid anhydride group, diamine (a2) and monoamine (a2 ′). In the case of synthesizing by the above, the total number of moles of the compound (a1) having two or more acid anhydride groups and the compound (a1 ′) having one acid anhydride group, the diamine (a2) and the monoamine (a2 ′) ) And the compound (a1) having the same number of moles and having two or more acid anhydride groups are in excess by mole with respect to the monoamine (a2 ′), and the diamine (a2) is an acid anhydride group. It is used so that it is in an excess amount by the number of moles relative to the compound (a1 ′) having one of the above. Then, in a system in which diamine (a2) and monoamine (a2 ′) coexist, compound (a1) having two or more acid anhydride groups is first introduced, and when it becomes stable, then acid anhydride groups A compound (a1 ′) having one of In this case, a polyamic acid (B1) having a group represented by the above formulas (21) and (22) at the molecular end is obtained.

[1.3 Reaction solvent]
As described above, the polyamic acid (B1) of the present invention includes at least one monomer selected from the group consisting of the compound (a1 ′) having one acid anhydride group and the monoamine (a2 ′), an acid anhydride group. Can be obtained by copolymerizing the compound (a1) having two or more and the diamine (a2), and the copolymerization is usually carried out in the presence of a reaction solvent. The reaction solvent used for obtaining the polyamic acid (B1) is not particularly limited as long as the polyamic acid (B1) 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-methyl-2-pyrrolidone, and N, N-dimethyl And acetamide.

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.
The reaction solvent is at least one monomer selected from the group consisting of compound (a1 ′) having one acid anhydride group and monoamine (a2 ′), compound (a1) having two or more acid anhydride groups, and Use of 100 parts by weight or more with respect to 100 parts by weight of the diamine (a2) is preferable because the reaction mixture containing the polyamic acid (B1) and the reaction solvent does not become too high and the reaction proceeds smoothly.

A method for producing the polyamic acid (B1) will be described below.
The order of addition of the polyamic acid (B1) raw material to the reaction system is not particularly limited. That is, at least one monomer selected from the group consisting of a compound (a1 ′) having one acid anhydride group and a monoamine (a2 ′), a compound (a1) having two or more acid anhydride groups, and a diamine ( a method of simultaneously adding a2) to a reaction solvent, a compound having two or more acid anhydride groups after adding diamine (a2) and monoamine (a2 ′) to the reaction solvent and dissolving them (a1)
), If necessary, a method of adding a compound (a1 ′) having one acid anhydride group, a compound (a1) having two or more acid anhydride groups, and a compound (a1 ′) having one acid anhydride group ) Is added to the reaction solvent and dissolved, then the monoamine (a2 ′) is added and reacted, and then the diamine (a2) is further added, and the compound (a1) having two or more acid anhydride groups and A diamine (a2) is added to a reaction solvent and reacted to synthesize a copolymer, and then the copolymer comprises a compound (a1 ′) having one acid anhydride group and a monoamine (a2 ′). Any method such as a method of adding at least one monomer selected from the group can be used. In addition, as a reaction solvent, you may use what added the below-mentioned alkenyl substituted nadiimide (C) previously. Moreover, you may add the below-mentioned alkenyl substituted nadiimide (C) at the arbitrary timings during manufacture of a polyamic acid (B1).

The reaction temperature for producing the polyamic acid (B1) is usually 0 ° C to 100 ° C, preferably 8 ° C to 70 ° C, and the reaction time is usually 0.2 to 20 hours, preferably 2 hours to 10 ° C. It's time.

The weight average molecular weight of the polyamic acid (B1) can be adjusted to 25,000 to 50,000, for example, by the following method.
Usually, the termination of polymerization by introduction of a molecular end group has the effect of reducing the molecular weight of the polymer compound, so the compound (a1 ′) having one monoamine (a2 ′) and one acid anhydride group forming the molecular end group The weight average molecular weight can be adjusted by adjusting the amount. That is, by increasing the amount of the monoamine (a2 ′) forming the molecular end group and the compound (a1 ′) having one acid anhydride group, the thermosetting composition can be reduced in molecular weight. The solubility in a solvent can be improved. On the other hand, it is possible to increase the molecular weight of the thermosetting composition by reducing the introduction amount of the monoamine (a2 ′) forming the molecular end group and the compound (a1 ′) having one acid anhydride group. And the mechanical strength of the resulting polyimide film can be improved.

[1.4 Explanation of each component for obtaining polyamic acid (B1)]
Hereinafter, the compound (a1 ′) having one acid anhydride group, the monoamine (a2 ′), and the compound (a1) having two or more acid anhydride groups that can be used to obtain the polyamic acid (B1) And diamine (a2) will be described.

[1.4 (1) Compound (a1) having two or more acid anhydride groups]
Compound having two or more acid anhydride groups used for obtaining polyamic acid (B1) (a
1) is not particularly limited as long as it has two or more acid anhydride groups. For example, an anhydride group such as a styrene-maleic anhydride copolymer, a methyl methacrylate-maleic anhydride copolymer, or the like. And a copolymer of a radically polymerizable monomer having a hydrogen atom and another radically polymerizable monomer, tetracarboxylic dianhydride, and the like. In addition, as tetracarboxylic dianhydride, the tetracarboxylic dianhydride represented by following formula (11) is used normally.

(In Formula (11), R ³ is an organic group having 2 to 100 carbon atoms.)
Examples of the tetracarboxylic dianhydride include 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, and 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, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), ethane Tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. Examples of tetracarboxylic dianhydrides also include compounds represented by the following formulas (b1-1) to (b1-73).

Examples of the compound (a1) having two or more acid anhydride groups include styrene-maleic anhydride copolymers, formulas (b1-1), (b1-5), (b1-6), (b1-7 ), (B1-8), (b1-9), (b1-14), (b1-18), (b1-20) are highly soluble in the reaction solvent, and the polyamic acid ( B1) is preferable because it can be suitably produced.

  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.

The compound (a1) having two or more acid anhydride groups may be used alone or in combination of two or more.
[1.4 (2) Diamine (a2)]
The diamine (a2) used for obtaining the polyamic acid (B1) is not particularly limited as long as it has two amino groups, but a diamine represented by the following formula (12) is usually used. It is done.

(In Formula (12), R ⁴ is an organic group having 2 to 100 carbon atoms.)
Examples of the diamine (a2) include p-phenylenediamine, m-phenylenediamine, p-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-1,2-diphenylethane, and 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-amino-2-methylphenoxy) ) 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, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane. Examples of the diamine (a2) also include compounds represented by the following formulas (II) to (VIII).

(In the formula (II), A ¹ is — (CH ₂ ) _m —, where m is an integer of 1 to 6,
In formulas (IV), (VI), and (VIII), A ¹ represents a single bond, —O—, —S—, —SS—
, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, — (CH ₂ ) _m —, —O— (CH ₂ ) _M —O—, or —S— (CH ₂ ) _m —S—, where m is an integer from 1 to 6;
In formulas (VII) and (VIII), A ² is each independently a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or It is C1-C3 alkylene.

In formulas (II) to (VIII), hydrogen bonded to a cyclohexane ring or a benzene ring may be replaced with -F or -CH ₃ . )
Examples of the compound represented by the formula (II) include diamines represented by the following formulas (II-1) to (II-3).

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

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

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

Examples of the compound represented by the formula (VI) include diamines represented by the following formulas (VI-1) to (VI-31).

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

Examples of the compound represented by the formula (VIII) include diamines represented by the following formulas (VIII-1) to (VIII-12).

As the diamine (a2), compounds represented by the formulas (II) to (VIII) are preferable, and more preferably, the formulas (V-1) to (V-5) and the formulas (VI-1) to (VI-) 12), Formula (VI-26), Formula (VI-27),
It is represented by Formula (VI-31), Formula (VII-1), Formula (VII-2), Formula (VII-6), Formula (VIII-1) to (VIII-5), Formula (VIII-12) Diamines represented by formulas (VI-1) to (VI-12), formula (VI-31), and formula (VIII-12) are more preferred.

  Another example of the diamine (a2) used in the present invention is a diamine represented by the following formula (IX).

(In Formula (IX), A ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _m — (wherein m is 1 to 6). R ⁶⁰ is hydrogen, a group having a steroid skeleton, a group represented by the following formula (X), an alkyl having 1 to 30 carbons (provided that A ³ is bonded) The positional relationship between the two amino groups bonded to is para or meta, or phenyl (however, the positional relationship between the two amino groups bonded to the benzene ring to which A ³ is bonded is the meta position. In the alkyl, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, ₃ may be replaced by -CH ₂ F, -CHF ₂ or -CF _3, also ring formation phenyl Hydrogen bonded to oxygen _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, may be replaced with -OCHF ₂ or -OCF _3.)

(In 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 carbon atoms. Yes,
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 hydrogen, —F, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ . Yes,
i 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 formula (IX), the two amino groups are bonded to the phenyl ring carbon, but the relationship between the bonding positions of the two amino groups is preferably the meta position or the para position. Each two additional amino group, "R ⁶⁰ -A ³ -" 3-position when the 1-position of the bond position of the 5-position, or 2 position and is preferably bonded to the 5-position.

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

In the above formulas (IX-1), (IX-2), (IX-7) and (IX-8), R ¹⁸ is preferably alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons. More preferably, it is C5-C12 alkyl or C5-C12 alkoxy. In the above formulas (IX-3) to (IX-6) and (IX-9) to (IX-11), R ¹⁹ is hydrogen, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons. It is preferable that it is C3-C10 alkyl or C3-C10 alkoxy.

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

In the above formulas (IX-12) to (IX-15), R ²⁰ is preferably hydrogen and alkyl having 4 to 16 carbon atoms, more preferably alkyl having 6 to 16 carbon atoms. In the formula (IX-16) and the formula (IX-17), R ²¹ is preferably hydrogen and alkyl having 6 to 20 carbon atoms, more preferably alkyl having 8 to 20 carbon atoms.

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

(IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31), In (IX-36) and (IX-37), R ²² is preferably hydrogen, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons, and alkyl having 3 to 12 carbons or 3 to 3 carbons. More preferably, it is 12 alkoxy. In addition, the above formulas (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX-35) ) And (IX-38), R ²³ is hydrogen, -F, alkyl having 1 to 12 carbons,
12 alkoxy, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ , preferably alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons. In the above formulas (IX-33) and (IX-34), A ⁹ is alkylene having 1 to 12 carbons.

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

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

Another example of the diamine (a2) used in the present invention includes compounds represented by the following formulas (XI) and (XII).

In formulas (XI) and (XII), R ¹⁰ is hydrogen or —CH ₃ , R ¹¹ is independently hydrogen, alkyl or alkenyl having 1 to 20 carbon atoms, and A ⁶ is independently A bond, —C (═O) — or —CH ₂ —; In the formula (XII), R ¹³ and R ¹⁴ are each independently hydrogen, alkyl having 1 to 20 carbons, or phenyl.

In the formula (XI), one of two “NH ₂ —Ph—A ⁶ —O—” (where Ph represents phenylene) is bonded to the 3rd position of the steroid nucleus, and the other is positioned to the 6th position. Bonding is preferred. 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 compound represented by the formula (XI) include diamines represented by the following formulas (XI-1) to (XI-4).

In formula (XII), two “NH ₂ — (R ¹⁴ —) Ph—A ⁶ —O—” (where Ph represents phenylene) are each bonded to a phenyl ring carbon, Is bound to carbon in the meta or para position relative to the carbon to which the steroid nucleus is bound. 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 formula (XII) include diamines represented by the following formulas (XII-1) to (XII-8).

  Another example of the diamine (a2) used in the present invention includes compounds represented by the following formulas (XIII) and (XIV).

In the formula (XIII), R ¹⁵ is hydrogen or alkyl having 1 to 20 carbons, and in the alkyl, any —CH ₂ — of the alkyl having 2 to 20 carbons is —O—, —CH═CH—. Or -C≡
C ⁷ may be substituted, A ⁷ is each independently —O— or alkylene having 1 to 6 carbons, A ⁸ is a single bond or alkylene having 1 to 3 carbons, and ring T is 1, 4-phenylene or 1,4-cyclohexylene, and h is 0 or 1. )

In the formula (XIV), R ¹⁶ is alkyl having 6 to 22 carbon atoms, and R ¹⁷ is hydrogen or 1 to carbon atoms.
22 alkyl, and each A ⁷ is independently —O— or alkylene having 1 to 6 carbons.

In the formula (XIII), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or para to A ⁷ .
Examples of the compound represented by the formula (XIII) include diamines represented by the following formulas (XIII-1) to (XIII-9).

In the above formulas (XIII-1) to (XIII-3), R ²⁴ is preferably hydrogen or alkyl having 1 to 20 carbon atoms, and in (XIII-4) to (XIII-9), R ²⁵ is hydrogen or It is preferable that it is a C1-C10 alkyl.

In the formula (XIV), 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 ⁷ .
Examples of the compound represented by the formula (XIV) include diamines represented by the following formulas (XIV-1) to (XIV-3).

In the formulas (XIV-1) to (XIV-3), R ²⁶ is preferably an alkyl having 6 to 20 carbon atoms, and R ²⁷ is more preferably hydrogen or an alkyl having 1 to 10 carbon atoms.
As described above, as the diamine (a2) used in the present invention, for example, diamines represented by the 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. For example, a compound represented by the following formula (XV) can be used in the present invention.

(In the above general formula (XV), R ¹³⁰ and R ¹⁴⁰ are each independently alkyl or phenyl having 1 to 3 carbon atoms, R ¹⁵⁰ is each independently phenylene substituted with methylene, phenylene or alkyl, x Are each 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.)
Another example of the diamine (a2) used in the present invention includes diamines represented by the following formulas (XVI-1) to (XVI-8).

In the above formulas (XVI-1) to (XVI-8), R ³⁰ is independently alkyl having 3 to 20 carbon atoms, and the formulas (XVI-3), (XVI-4), (XVI-6) and In (XVI-8), R ³¹ is independently alkyl having 3 to 20 carbons.

  In addition, the diamine (a2) that can be used in the present invention is not limited to the diamine of the present specification, and various other forms of diamine may be used within the scope of achieving the object of the present invention. it can.

  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.

Moreover, although high transparency is required depending on the use of the thermosetting composition, in such a case, 3,3′-diaminodiphenylsulfone, 2,2-bis [4- (4-amino- 2-
It is particularly preferred to use methylphenoxy) phenyl] propane and diamines where y = 1 to 15 in the general formula (XV) above.

[1.4 (3) Compound (a1 ′) having one acid anhydride group]
Compound (a1 ′) having one acid anhydride group used for obtaining polyamic acid (B1)
) Is not particularly limited as long as it has one acid anhydride group in the molecule. For example, a compound represented by the following formula (13) is used.

(In Formula (13), R < ⁶ > is a C2-C100 organic group.)
Specific examples of the dicarboxylic acid anhydride represented by the formula (13) include trimethoxysilylpropyl succinic anhydride, triethoxysilylpropyl succinic anhydride, methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilyl. Propyl succinic anhydride, trimethoxysilyl butyl succinic anhydride, triethoxysilyl butyl succinic anhydride, methyldiethoxysilyl butyl succinic anhydride, p- (trimethoxysilyl) phenyl succinic anhydride, p- ( Triethoxysilyl) phenyl succinic anhydride, p- (methyldimethoxysilyl) phenyl succinic anhydride, p- (methyldiethoxysilyl) phenyl succinic acid Hydride, m- (trimethoxysilyl) phenyl succinic anhydride, m- (triethoxysilyl) phenyl succinic anhydride, m- (methyldiethoxysilyl) phenyl succinic anhydride, maleic anhydride, citraconic anhydride You can list things.

  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 anhydride, m- (triethoxysilyl) phenyl succinic anhydride, trimethoxysilylpropyl succinic anhydride and triethoxysilylpropyl succinic anhydride are preferred, triethoxysilylpropyl succinic anhydride, maleic anhydride And citraconic anhydride are preferred, and maleic anhydride and citraconic anhydride are more preferred.

When the polycarboxylic acid (B1) is obtained by copolymerization and the dicarboxylic acid anhydride represented by the formula (13) is used, the polyamic acid (B1) is represented by the formula (22). Has molecular end groups. In addition, when maleic anhydride is used as the dicarboxylic acid anhydride represented by the formula (13), it has a molecular end group represented by the following formula (23), and when citraconic anhydride is used, the following formula ( It has a molecular end group represented by 24) or (25).

These compounds having one acid anhydride group (a1 ′) can be used singly or in combination of two or more.
[1.4 (4) Monoamine (a2 ′)]
The monoamine (a2 ′) used for obtaining the polyamic acid (B1) is not particularly limited, and examples of the monoamine (a2 ′) preferably used in the present invention include compounds represented by the following formula (14). .

(In Formula (14), R ⁵ is an organic group having 2 to 100 carbon atoms.)
Specific examples of the compound represented by the formula (14) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4 -Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p- Mention may be made of aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenyltriethoxysilane and m-aminophenylmethyldiethoxysilane.

  Among these, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, m-aminophenyltrimethoxysilane, m-amino are preferred because the film formed from the thermosetting composition has excellent durability. Phenyltriethoxysilane, 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.
[1.5 Polyamic acid (B2)]
The polyamic acid (B2) has a structural unit represented by the following formula (2), a group represented by the following formula (23), a group represented by the following formula (24), and a group represented by the following formula (25). A thermosetting composition which is a polyamic acid having at least one molecular end group selected from the group consisting of:

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.)
The polyamic acid (B2) contained in the thermosetting composition of the present invention preferably has a weight average molecular weight of 1,000 to 50,000.

  The polyamic acid (B2) used in the present invention is usually at least one monomer selected from the group consisting of maleic anhydride or citraconic anhydride, a compound (a1) having two or more acid anhydride groups, and a diamine (a2 ) Is copolymerized, but is not limited to the polyamic acid (B2) obtained by the production method, and the polyamic acid (B2) obtained by another production method may be used.

[1.6 Reaction Conditions for Obtaining Polyamic Acid (B2)]
The polyamic acid (B2) is a copolymer of at least one monomer selected from the group consisting of maleic anhydride or citraconic anhydride, a compound (a1) having two or more acid anhydride groups, and a diamine (a2). Can be obtained. The amount of each monomer is from the group consisting of 0.6 to 0.999 mol of compound (a1) having two or more acid anhydride groups and 1 mol of diamine (a2) and maleic anhydride or citraconic anhydride. It is preferable to use 0.002 to 0.8 mol of at least one selected monomer, and the compound (a1) having two or more acid anhydride groups with respect to 1 mol of the diamine (a2) 0.8 to 0. It is more preferable to use 0.02 to 0.4 mol of at least one monomer selected from the group consisting of 99 mol and maleic anhydride or citraconic anhydride.

[1.7 Reaction solvent]
As described above, the polyamic acid (B2) of the present invention includes at least one monomer selected from the group consisting of maleic anhydride or citraconic anhydride, a compound (a1) having two or more acid anhydride groups, and a diamine. Although it can be obtained by copolymerizing (a2), the copolymerization is usually carried out in the presence of a reaction solvent. The reaction solvent used for obtaining the polyamic acid (B2) is not particularly limited as long as the polyamic acid (B2) can be synthesized. For example, the same reaction solvent as that used for obtaining the polyamic acid (B1) is used. Is mentioned.

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.
The reaction solvent is 100 parts by weight in total of at least one monomer selected from the group consisting of maleic anhydride or citraconic anhydride, compound (a1) having two or more acid anhydride groups, and diamine (a2). If used in an amount of 100 parts by weight or more, the viscosity of the reaction mixture containing the polyamic acid (B2) and the reaction solvent does not become too high, and the reaction proceeds smoothly, which is preferable.

A method for producing the polyamic acid (B2) will be described below.
The order of addition of the polyamic acid (B2) raw material to the reaction system is not particularly limited. That is, a method of simultaneously adding at least one monomer selected from the group consisting of maleic anhydride or citraconic anhydride, a compound (a1) having two or more acid anhydride groups, and a diamine (a2) to the reaction solvent, A compound (a1) having two or more acid anhydride groups and a diamine (a2) are added to a reaction solvent and reacted to synthesize a copolymer, and then the maleic anhydride or citraconic anhydride is added to the copolymer. Any method such as a method of adding at least one monomer selected from the group consisting of products can be used. In addition, as a reaction solvent, you may use what added the below-mentioned alkenyl substituted nadiimide (C) previously. Moreover, you may add the below-mentioned alkenyl substituted nadiimide (C) at the arbitrary timings during manufacture of a polyamic acid (B2).

  The reaction temperature for producing the polyamic acid (B2) is usually 0 ° C. to 100 ° C., preferably 8 ° C. to 70 ° C., and the reaction time is usually 0.2 to 20 hours, preferably 2 hours to 10 ° C. It's time.

[1.8 Explanation of each component for obtaining polyamic acid (B2)]
In order to obtain the polyamic acid (B2), at least one monomer selected from the group consisting of maleic anhydride or citraconic anhydride, a compound (a1) having two or more acid anhydride groups and a diamine (a2) Use.

  As the compound (a1) having two or more acid anhydride groups used for obtaining the polyamic acid (B2), a compound (a1) having two or more acid anhydride groups used for obtaining the polyamic acid (B1) The same as those listed above are used.

  As the diamine (a2) used for obtaining the polyamic acid (B2), the same diamine (a2) as used for obtaining the polyamic acid (B1) can be used.

[1.9 Weight Average Molecular Weight of Polyamic Acid (B2)]
The polyamic acid (B2) used in the present invention preferably has a weight average molecular weight of 100,000 or less. Within this range, a thermosetting composition that is excellent in solubility in a solvent and can be applied by a dispenser coating method or the like can be obtained. Further, from the viewpoint of solubility of the polyamic acid (B2) in the solvent, the weight average molecular weight of the polyamic acid (B2) is more preferably 50,000 or less, further preferably 45,000 or less, Most preferably, it is 000 or less. On the other hand, from the viewpoint of mechanical strength of the resulting polyimide film, it is more preferably 25,000 or more.

When the weight average molecular weight of the polyamic acid (B2) is 100,000 or less, the solubility in a solvent is excellent, and the concentration of the polyamic acid (B2) dissolved in the solvent can be increased. Therefore, it is possible to increase the film thickness of the polyimide film obtained by applying a curing treatment by heating to the coating film formed by applying the thermosetting composition, which is suitable as a thermosetting composition. is there.

  In addition, the weight average molecular weight of the polyamic acid (B2) used for this invention can be measured by a gel permeation chromatography (GPC) method. Specifically, the polyamic acid (B2) is diluted with tetrahydrofuran (THF) or the like to a concentration of about 1% by weight, and THF is used as a developing agent using columns G4000HXL, G3000HXL, G2500HXL and G2000HXL manufactured by Tosoh Corporation. As measured by gel permeation chromatography (GPC) and converted to polystyrene.

[2 Alkenyl Substituted Nadiimide Compound (C)]
The alkenyl-substituted nadiimide compound (C) contained in the thermosetting composition of the present invention is not particularly limited as long as it is a compound having at least one alkenyl-substituted nadiimide structure in the molecule, but preferably is represented by the following formula (5) The compounds represented are used.

(In formula (5), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, 6 to 12 carbon atoms Either aryl or benzyl, n is 1 or 2,
When n = 1, Q is hydrogen, hydroxyl group, alkyl having 1 to 12 carbon atoms, alkenyl having 1 to 3 carbon atoms, hydroxyalkyl having 1 to 12 carbon atoms, hydroxyalkenyl having 2 to 12 carbon atoms, or 5 to 5 carbon atoms. Cycloalkyl having 8 carbon atoms, hydroxycycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, — [(C _q H _2q ) O _t (C _r H _2r O) _u C _s H _2s X] A group represented by the formula (wherein q, r, and s are each independently an integer of 2 to 6, t is 0 or 1, u is an integer of 0 to 30, and X is hydrogen or a hydroxyl group),-( R) _a group represented by _a- C ₆ H ₄ -R ⁴¹ (where a is 0 or 1, R is alkylene having 1 to 4 carbon atoms, R ⁴¹ is hydrogen or alkyl having 1 to 4 carbon atoms) _{), - C 6 H 4 -T} -C 6 H 5 , a group represented by the table in _{-C 6 H 4 -T-C 6} H 4 -OH Group (wherein, T is _{-CH 2 -, - C (CH} 3) 2 -, isopropylidene, -CO -, - S- or -SO ₂ - in which), or their groups containing an aromatic ring In the case, 1 to 3 hydrogen atoms directly bonded to the aromatic ring are groups substituted with a hydroxyl group,
When n = 2, Q is alkylene having 2 to 20 carbons, cycloalkylene having 5 to 8 carbons,-[(C _q H _2q O) _t (C _r H _2r O) _u C _s H _2s ]- A group represented by the formula (wherein q, r and s are each independently an integer of 2 to 6, t is 0 or 1, u is an integer of 1 to 30), an arylene having 6 to 12 carbon atoms,-( R) _a group represented by _a —C ₆ H ₄ —R ⁵¹ — (wherein, a is 0 or 1, R and R ⁵¹ each independently represent alkylene having 1 to 8 carbons, or cyclohexane having 1 to 8 carbons) A group represented by —C ₆ H ₄ —TC ₆ H ₄ — (wherein T represents —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—). , —OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ O—, —S—, —SO ₂ —), or when these groups contain an aromatic ring, 3 hydrogens Is a group that has been replaced by a hydroxyl group. )
The compound represented by the formula (5) 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 sometimes simply referred to as “bisalkenyl-substituted nadiimide”).

  In the present invention, as the alkenyl-substituted nadiimide compound (C), it is preferable to use a compound represented by the above formula (5). As the alkenyl-substituted nadiimide (C), n is 1 in the above formula (5). In the compound and the above formula (5), it is preferable to use a compound in which n is 2, or in the above formula (5), a compound in which n is 2.

That is, the thermosetting composition of the present invention is preferably a thermosetting composition containing a compound in which n is 2 in the above formula (5). In the above formula (5), as the compound in which n is 2, Q is an alkylene having 2 to 10 carbon atoms, a group represented by — (R) _a —C ₆ H ₄ —R ⁵¹ — (wherein a is 0 or 1, R and R ⁵¹ are each independently alkylene having 1 to 4 carbon atoms, or a group represented by —C ₆ H ₄ —T—C ₆ H ₄ — (wherein T is —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ O—, —S—, —SO ₂ — ) Is preferred. In the above formula (5), as the compound in which n is 2, R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, Q is — (CH ₂ ) ₆ —, A compound that is a group represented by (6) or a group represented by formula (7) is more preferred.

Further, as the alkenyl-substituted nadiimide compound (C), a compound in which n is 1 in the above formula (5) and a compound in which n is 2 in the above formula (5) may be used in combination. When used in combination, the alkenyl-substituted nadiimide compound (C) is n1 in the above formula (5), and Q is alkyl having 1 to 12 carbons, cycloalkyl having 5 to 8 carbons, or 6 to 12 carbons. Aryl, benzyl, a group represented by — [(C _q H _2q ) O _t (C _r H _2r O) _u C _s H _{2s + 1} ] (where q, r and s are each independently 2 to 6 , T is 0 or 1, u is an integer of 1 to 30, and a group represented by-(R) _a -C ₆ H ₄ -R ⁴¹ (where a is 0 or 1, R is Alkylene having 1 to 4 carbon atoms, R ⁴¹ represents hydrogen or alkyl having 1 to 4 carbon atoms, or a group represented by —C ₆ H ₄ —T—C ₆ H ₅ (wherein T represents —CH _2- , —C (CH ₃ ) ₂ —, —CO—, —S— or —SO ₂ —), and the formula (5) And at least one compound in which n is 2. Further, as the alkenyl-substituted nadiimide compound (C), in the above formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 1, Q is 1 carbon atom At least one compound which is -12 alkyl, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms or benzyl, and at least one compound wherein n is 2 in the formula (5), It is more preferable to contain.

Further, the alkenyl substituted nadiimide compound as (C), the formula (5) R ¹ and R ² in are each independently hydrogen or alkyl of 1 to 6 carbon atoms, n is 1, Q is 1 to carbon atoms At least one compound which is 12 alkyls or aryls having 6 to 12 carbon atoms, and in the formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and n is 2 Q is — (CH ₂ ) ₆ —, a group represented by formula (6) or a formula (
It is more preferable that at least one compound which is a group represented by 7) is included.

  Here, the thermosetting composition of the present invention comprises at least one compound in which n is 1 in the above formula (5) and at least one compound in which n is 2 in the above formula (5). When it is included, 1.0 to 100.0 moles of the compound in which n is 2 with respect to 1.0 mole of the compound in which n is 1, preferably n with respect to 1.0 mole of the compound in which n is 1 1.0 to 50.0 mol of the compound in which is 2 is used.

[2.1 Alkenyl-substituted nadiimide (c1)]
Specific examples of the alkenyl-substituted nadiimide compound (alkenyl-substituted nadiimide (c1)) in which n is 1 in the compound represented by the above formula (5) include the following.

Specific examples of the alkenyl-substituted nadiimide (c1) include
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.

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.

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,
Is mentioned.

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.

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,
Is mentioned.

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,
Is mentioned.

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,
Is mentioned.

Moreover, as said alkenyl substituted nadiimide (c1), as a preferable thing,
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.

Moreover, as said alkenyl substituted nadiimide (c1), as a preferable thing,
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.
As the alkenyl-substituted nadiimide (c1), 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.

[2.2 Bisalkenyl-substituted nadiimide (c2)]
Specific examples of the alkenyl-substituted nadiimide compound (bisalkenyl-substituted nadiimide (c2)) in which n is 2 in the compound represented by the above formula (5) include the following.

Specific examples of bisalkenyl-substituted nadiimide (c2) include
N, N′-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide),
N, N′-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2
, 3-dicarboximide),
N, N′-ethylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide),
N, N′-trimethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide),
N, N′-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2
, 3-dicarboximide),
N, N′-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-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-
En-2,3-dicarboximide),
Is mentioned.

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,
Is mentioned.

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),
Is mentioned.

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,
Is mentioned.

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,
Is mentioned.

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

Also,
1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene,
N, N′-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2.2.1
] Hept-5-ene-2,3-dicarboximide),
N, N′-m- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),
N, N′-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide),
N, N′-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide),
Is mentioned.

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

  Further, the following may be included including asymmetric alkylene phenylene.

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

  When the compound represented by the above formula (5) is used as the alkenyl-substituted nadiimide compound (C) contained in the thermosetting property of the present invention, the compound is a low molecular weight imide monomer having a bulky structure. It is soluble in most organic solvents and can be used stably without crystal precipitation or gelation even when stored in solution for a long period of time. 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.

[3 Solvent (D)]
The thermosetting composition of the present invention contains the above-mentioned polyamic acid (B) and alkenyl-substituted nadiimide compound (C), and usually further contains a solvent (D). By containing a solvent (D), it becomes easy to adjust the viscosity of a thermosetting composition, and it can apply | coat to a board | substrate suitably by coating methods, such as a dispenser coating method.

  The thermosetting composition of the present invention can be obtained, for example, by dissolving the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C) in a solvent (D). Therefore, the solvent contained in the thermosetting composition of the present invention is not particularly limited as long as it can dissolve the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C).

  Even if the solvent alone does not dissolve the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C), the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C) can be dissolved by mixing with another solvent. Solvents that can be used can also be used as solvent (D).

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, Examples include dioxane, ethylene glycol, propylene glycol, glycerin, and cyclohexanone.

  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.
[4 Solid content concentration of thermosetting composition of the present invention]
In the present invention, the total concentration (solid content concentration) of the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C) in the thermosetting composition is not particularly limited. It is preferably 45 to 99% by weight, more preferably 50 to 90% by weight, and still more preferably 55 to 85% by weight. The concentration range is preferable because the thickness of the coating film obtained by one dispenser application using the thermosetting composition is optimized. Furthermore, it is preferable because curing shrinkage and warping of the substrate hardly occur when the coating film is cured.

  In the present invention, the concentration of the polyamic acid (B) in the thermosetting composition is not particularly limited. The polyamic acid (B) is preferably 0.01 to 50% by weight, and more preferably 10 to 30% by weight, based on 100% by weight of the entire thermosetting composition. When the concentration is within the above range, it is preferable that 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. However, when the entire thermosetting composition is 100% by weight, it is preferably 30 to 70% by weight, and 45 to 60% by weight. % Is more preferable. It is preferable for the concentration to be in the above-mentioned concentration range because good characteristics can be imparted as an insulating film to the polyimide film obtained from the thermosetting composition of the present invention.

  When using as a thermosetting composition, since the film thickness of the polyimide film obtained becomes thick, so that the density | concentration of a polyamic acid (B) and an alkenyl substituted nadiimide compound (C) is high, it is preferable. 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.

[5 Additives added to the thermosetting composition of the present invention]
The thermosetting composition of the present invention can be obtained by mixing the polyamic acid (B), the alkenyl-substituted nadiimide compound (C), and, if necessary, the solvent (D).

  Furthermore, depending on the intended characteristics, the thermosetting composition of the present invention may contain other components other than the above components. Other ingredients include epoxy resins, acrylic resins, surfactants, antistatic agents, coupling agents, epoxy curing agents such as trimellitic acid, aminosilicon compounds, pH adjusters, rust preventives, antiseptics, and antifungal agents. And additives such as additives, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, water-soluble polymers, pigments and dyes. Other components are added as necessary, and a thermosetting composition containing the additive can be obtained by uniformly mixing and dissolving them.

[5 (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 55% by weight, more preferably 1 to 40% by weight based on 100% by weight of the entire thermosetting composition. . 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. It is done.

  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 and N-phenylmaleimide.

  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 ', mention may be made of N'- tetraglycidyl-4,4'-diaminodiphenylmethane.

  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.
[5 (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, When the whole thermosetting composition is 100 weight%, 0.1-20 weight% is preferable and 1-10 weight% is 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 monomer include a monofunctional polymerizable monomer having hydroxyl, a monofunctional polymerizable monomer having no hydroxyl, a bifunctional (meth) acrylate, and a polyfunctional (meth) acrylate having three or more functions. .

  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 Mention may be made of (meth) acrylates. 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 Acrylate can be mentioned.

  Specific examples of trifunctional or higher polyfunctional (meth) acrylates are trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, diglycerin tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta Rithritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, Mention may be made of ethylene oxide-modified tri (meth) acrylate phosphate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, or urethane (meth) acrylate.

The acrylic resin can be obtained by polymerization using at least one of the above monomers.
These acrylic resins may be used alone or in combination of two or more.

[5 (3) Surfactant]
A surfactant may be added to the thermosetting composition of the present invention in order to improve the wettability, leveling property, or coating property of the thermosetting composition to the base substrate. 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 amount of the surfactant is preferably 0.01 to 1% by weight when the entire thermosetting composition is 100% by weight.

[5 (4) Antistatic agent]
An antistatic agent may be added to the thermosetting composition of the present invention in order to prevent the thermosetting composition from being charged. 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 amount of the antistatic agent is preferably 0.01 to 1% by weight when the entire thermosetting composition is 100% by weight.

[5 (5) Coupling agent]
A coupling agent may be added to the thermosetting composition of the present invention. 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 can be exemplified. 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 contained in an amount of 0.01 to 3% by weight based on 100% by weight of the entire thermosetting composition.

[5 (6) Epoxy curing agent]
When an epoxy resin is contained in the thermosetting composition of the present invention, it is preferable that an epoxy curing agent is further contained. The epoxy curing agent 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 contained in an amount of 0.2 to 5% by weight when the entire thermosetting composition is 100% by weight.
[5 (7) Aminosilicon compound]
An aminosilicon compound may 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 for improving the adhesion to the substrate, and is preferably contained in an amount of 0.05 to 2% by weight when the entire thermosetting composition is 100% by weight.

[6 Method for producing thermosetting composition]
Examples of the method for producing the thermosetting resin composition of the present invention include a method of mixing a solution containing polyamic acid (B) and a solution containing alkenyl-substituted nadiimide (C), alkenyl-substituted nadiimide (C) and solvent (D ) In the presence of a polyamic acid (B).

  In the case of the method of mixing the solution containing the polyamic acid (B) and the solution containing the alkenyl-substituted nadiimide (C), the solution containing the alkenyl-substituted nadiimide (C) is added to the solution containing the polyamic acid (B). ˜100 ° C., preferably 8 ° C. to 70 ° C., usually 0.2 to 20 hours, preferably 2 hours to 10 hours, and mixing until the viscosity of the thermosetting resin composition becomes uniform. It is done.

  In the case of synthesizing polyamic acid (B) in the presence of alkenyl-substituted nadiimide (C) and solvent (D), the thermosetting composition of the present invention is obtained by polymerizing polyamic acid at the reaction temperature and reaction time described above. Is obtained.

  When the polyamic acid (B) is synthesized in the presence of the alkenyl-substituted nadiimide (C) and the solvent (D), the viscosity of the resulting thermosetting composition can be easily adjusted and can be produced in one pot. Is preferable because it can be simplified.

  Specifically, a raw material monomer of polyamic acid (B) or a mixed solution of raw material monomers is added to a system in which alkenyl-substituted nadiimide (C) is dissolved in solvent (D). The order in which the raw material monomers are added is not particularly limited, and examples thereof are the same as in the case where the polyamic acid (B) is synthesized in advance.

  That is, as one aspect of the method for producing the thermosetting composition of the present invention, in the presence of an alkenyl-substituted nadiimide (C) and a solvent (D), a compound represented by the following formula (13) and the following formula (14) At least one monomer selected from the group consisting of the compounds represented, a compound represented by the following formula (11), and a compound represented by the following formula (12) are copolymerized to produce an alkenyl-substituted nadiimide (C) and the following formula ( 2) having a structural unit represented by 2), having a weight average molecular weight of 25,000 to 50,000, and comprising a group represented by the following formula (21) and a group represented by the following formula (22). A thermosetting composition comprising a polyamic acid (B1) having at least one selected molecular end group is obtained.

(In the formulas (2) and (11), R ³ is an organic group having 2 to 100 carbon atoms. In the formulas (2) and (12), R ⁴ is an organic group having 2 to 100 carbon atoms. In (13) and (22),
R ⁶ is an organic group having 2 to 100 carbon atoms, and in formulas (14) and (21), R ⁵ is an organic group having 2 to 100 carbon atoms. )
In addition, another embodiment of the method for producing the thermosetting composition of the present invention is selected from the group consisting of maleic anhydride and citraconic anhydride in the presence of alkenyl-substituted nadiimide (C) and solvent (D). At least one compound, a compound represented by the following formula (11) and a compound represented by the following formula (12) are copolymerized to have an alkenyl-substituted nadiimide (C) and a structural unit represented by the following formula (2). And a polyamide having at least one molecular end group selected from the group consisting of a group represented by the following formula (23), a group represented by the following formula (24), and a group represented by the following formula (25) A thermosetting composition containing the acid (B2) is obtained.

(In formulas (2) and (11), R ³ is an organic group having 2 to 100 carbon atoms, and in formulas (2) and (12), R ⁴ is an organic group having 2 to 100 carbon atoms.)
[7 Viscosity of thermosetting composition]
In the present invention, the viscosity of the thermosetting composition is preferably 51 to 50000 mPa · s (25 ° C.), more preferably 100, in that when dispensing is performed at room temperature, accuracy by a coating method using a dispenser is improved. It is -10000 mPa * s (25 degreeC), More preferably, it is 400-4000 mPa * s (25 degreeC). When the viscosity is 50000 mPa · s (25 ° C.) or less, the viscosity does not become too high, and the pressure to pressurize does not become too high, so that it can be discharged from the tip of the dispenser, and the viscosity is 51 mPa · s ( In the case of 25 ° C. or more, the viscosity of the thermosetting composition does not become too low, and it is practical without being wet spread on the coated substrate.

  In the present invention, in order to adjust the viscosity to 51 to 50000 mPa · s (25 ° C.), the concentration (solid content concentration) and solvent of the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C) in the thermosetting composition It is obtained by adjusting the amount of (D).

  When inkjet printing is performed at room temperature, the jetting accuracy is preferably 1 to 50 mPa · s (25 ° C.), more preferably 5 to 30 mPa · s (25 ° C.), and even more preferably 8 to 20 mPa. -S (25 ° C).

When jetting by heating the ink head, it is preferably 1 to 50 mPa · s, more preferably 5 to 30 mPa · s at the heating temperature (temperature at which the alkenyl-substituted nadiimide compound is not cured, preferably 40 to 120 ° C.). More preferably, it may be 8 to 20 mPa · s.

  When screen printing is performed at room temperature, it is preferably 500 to 50,000 mPa · s (25 ° C.), more preferably 1,000 to 30,000 mPa · s (25 ° C.), and further preferably 5,000 to 30. 1,000 mPa · s (25 ° C.).

When the viscosity is 500 mPa · s or more, a uniform coating film can be obtained without the thermosetting composition flowing out after printing. On the other hand, if the viscosity is 50,000 mPa · s or less, the transfer property of the thermosetting composition to the substrate is good, and the generation of voids and pinholes in the printed film can be suppressed.

[8 Polyimide film]
The polyimide film of the present invention is obtained by applying the above-mentioned thermosetting composition on a substrate to form a coating film, and then curing the coating film. In addition, formation of a coating film is normally performed by apply | coating the above-mentioned thermosetting composition on a board | substrate, and removing volatile compounds, such as a solvent (D), by drying, and hardening processing is usually Although it is performed by heating, it may be UV treatment, ion beam, electron beam, gamma ray treatment, or the like.

  It can be applied to the surface of the substrate, dried with a solvent, and then cured to form a polyimide film having a whole surface or a predetermined pattern (such as a line). Examples of the coating method include a dispenser coating method, a spinner method, a dipping method, and a dropping method, but a dispenser coating method is preferable in that a pattern-like (line-like) polyimide film can also be formed.

In the present invention, a patterned polyimide film is also referred to as a patterned polyimide film.
[8.1 Application of Thermosetting Composition]
Application by the dispenser application method, which is a preferable application method for obtaining the polyimide film of the present invention, applies a constant pressure to the syringe and discharges a predetermined amount of the thermosetting composition from the needle tip. 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.

[8.2 Solvent drying]
After applying the thermosetting composition of the present invention on a substrate by a dispenser coating method or the like, for example, by vaporizing a volatile compound such as a solvent (D) by heating using a hot plate or an oven. The film can be removed to form a coating film, that is, a film containing the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C).

  Heating conditions vary depending on the type and blending ratio of each component, but a temperature at which the polyamic acid (B) does not cure is preferable, usually 70 to 120 ° C. When using an oven, when using a hot plate for 5 to 60 minutes The coating film is formed in 1 to 30 minutes.

[8.3 Curing treatment of polyimide film]
After forming a film (coating film) containing the polyamic acid (B) and the alkenyl-substituted nadiimide compound (C), it is preferably 150 to 350 ° C., more preferably 200 to 200, for imidation of the polyamic acid (B). A polyimide film can be obtained by curing at 300 ° C. The heating time is 30 to 120 minutes when an oven is used, and 5 to 60 minutes when a hot plate is used.

When the coating film is formed in a pattern, a patterned polyimide film is formed. That is, in this specification, 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.

  The polyimide film that can be used in the present invention is preferably formed on a substrate such as a polyimide film, but is not particularly limited thereto, and can be formed on a known substrate.

  Specifically, as a substrate applicable to the present invention, for example, glass epoxy substrate, glass composite substrate, paper having various standards such as FR-1, FR-3, FR-4, CEM-3, or E668 A printed wiring board such as a phenol substrate, a paper epoxy substrate, a green epoxy substrate, or a BT resin substrate can be preferably used.

  Alternatively, other substrates applicable to the present invention include a substrate made of a metal such as copper, brass, phosphor bronze, beryllium copper, aluminum, gold, silver, nickel, tin, chromium, or stainless steel, or a metal on the substrate. Part (which may be a substrate having a metal surface thereof); aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), zirconium silicate (zircon), magnesium oxide (magnesia), titanium Aluminum oxide, barium titanate, lead titanate (PT), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), lithium niobate, lithium tantalate, cadmium sulfide, molybdenum sulfide, beryllium oxide ( Beryllia), silicon oxide (silica), silicon carbide (silicon carba G), silicon nitride (silicon nitride), boron nitride (boron nitride), zinc oxide, mullite, ferrite, steatite, holsterite, spinel, or ceramics on the substrate, or a ceramic portion on the substrate ( These may be substrates having a ceramic surface), PET (polyethylene terephthalate) resin, PBT (polybutylene terephthalate) resin, PCT (polycyclohexylene dimethylene terephthalate) resin, PPS (polyphenylene sulfide) resin, polycarbonate Resin, polyacetal resin, polyphenylene ether resin, polyamide resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, A substrate made of a resin such as a poxy resin, an acrylic resin, Teflon (registered trademark), a thermoplastic elastomer, or a liquid crystal polymer, or a resin portion on the substrate (may be a substrate having the surface of those resins) or silicon , Germanium, gallium arsenide, or other semiconductor substrates; glass substrates; or substrates on which electrode materials such as tin oxide, zinc oxide, ITO, or ATO are formed on the surface; α-gel, β Various substrates such as gel sheets such as gel, λ gel αGEL (alpha gel), βGEL (beta gel), θGEL (theta gel), or γGEL (gamma gel) (which is a registered trademark of Taika Co., Ltd.), wafers or sheets can be used.

[9 Film substrate]
The film substrate of the present invention may be a film substrate having a polyimide film obtained from the above-mentioned thermosetting composition, and is not particularly limited. For example, on a substrate such as a polyimide film in which wiring is formed in advance, The thermosetting composition of the present invention is applied to the entire surface or a predetermined pattern (line shape or the like) by a dispenser coating method, and then the substrate is dried and further heated, so that a part or the entire surface is insulative. A flexible film substrate coated with a polyimide film having the above can be obtained. The film substrate of the present invention can be used for electronic components such as flexible wiring boards.

[10 Silicon wafer substrate]
The silicon wafer substrate of the present invention is not particularly limited as long as it is a silicon wafer substrate having a polyimide film obtained from the above-mentioned thermosetting composition, for example, on a silicon wafer substrate on which wiring is formed in advance, By applying and applying the thermosetting composition of the present invention to the entire surface or a predetermined pattern (line shape or the like) by a dispenser coating method, the silicon wafer substrate is dried, and further heated, thereby providing an insulating property. It is possible to obtain a silicon wafer substrate coated with a polyimide film having The silicon wafer substrate of the present invention can be used for electronic components such as semiconductors.

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, compound (a1 ′) having one acid anhydride group, diamine (a2), alkenyl-substituted nadiimide (C), and solvent used in Examples and Comparative Examples The name of (D) is indicated by an abbreviation. This abbreviation is used in the following description.

<Compound (a1) having two or more acid anhydride groups>
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride <Compound having one acid anhydride group (a1 ′)>
MA: maleic anhydride CA: citraconic anhydride <diamine (a2)>
DDS: 3,3′-diaminodiphenylsulfone BAP: 2,2-bis [4- (4-amino-2methylphenoxy) phenyl] propane <Alkenyl-substituted nadiimide (C)>
BANIM: bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane BANIX: N, N′-m-xylylene-bis (allylbicyclo [2 2.1] hept-5-ene-2,3-dicarboximide)
<Solvent (D)>
GBL: γ-butyrolactone NMP: N-methyl-2-pyrrolidone EDM: diethylene glycol methyl ethyl ether The methods for measuring physical properties in the examples are as follows.

(i) Viscosity Viscosity was measured with an E-type viscometer (VISCONIC EHD manufactured by TOKYO KEIKI).
(ii) Molecular weight The sample was diluted with tetrahydrofuran (THF) so that the sample concentration was about 1% by weight, and JASCO GULLIVER 1500 (intelligent differential refractometer RI-1530) manufactured by JASCO Corporation was used as a GPC device. Measured by the GPC method using the diluted solution as 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.

  Since the polyamic acid peak and the alkenyl-substituted nadiimide peak can be clearly distinguished on the GPC chart, the weight average molecular weight was calculated from the polyamic acid peak portion in the case of a mixed solution of polyamic acid and alkenyl-substituted nadiimide.

(iii) Line width It observed with the optical microscope.
(iv) Film thickness A stylus-type film thickness meter α step 200 manufactured by KLA-Tencor Japan was used, and the average value of the measured values at three locations was defined as the film thickness.
(v) Dielectric constant, dielectric loss tangent, volume resistivity, withstand voltage, dielectric strength After applying 3 mL of ink on a chrome substrate and forming a thin film by spin coating, it is dried on a hot plate at 80 ° C. for 5 minutes, and 230 ° C. In an oven for 30 minutes to cure. Then, aluminum was vapor-deposited on the polyimide resin film shape, and the electrode was created.

The dielectric constant and dielectric loss tangent were measured using LCR METER (made by HEWLETT PACKERD).
Volume resistivity, withstand voltage, and dielectric strength were measured using ULTRAHIGH REISTANCE METER 4263B (manufactured by ADVANTEST).

[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 at room temperature for 3 hours under a dry nitrogen stream to obtain a brown polyamic acid 30% by weight solution. . The viscosity of this solution was 12000 mPa · s (25 ° C.). The weight average molecular weight measured by GPC was 25,540.

The raw materials were charged with ODPA 13.8 g, BAP 18.9 g, MA 0.3 g and GBL 77.0 g.
A 500 ml three-necked flask equipped with a stirrer and a raw material charging inlet was charged with raw materials as shown below and stirred at 60 ° C. for 1 hour under a dry nitrogen stream. Got.

The raw materials were charged 77.0 g of BANIX and 33.0 g of GBL.
110 g of the brown polyamic acid 30 wt% solution obtained above and 110 g of the alkenyl-substituted nadiimide 70 wt% solution were mixed to obtain a thermosetting composition (1). The viscosity of this composition was 3,800 mPa · s (25 ° C.).

The obtained thermoplastic resin composition (1) was tested as follows.
<Coating test>
The thermosetting composition (1) was sealed in a dispenser injection container equipped with a needle having a needle tip width of 1 mm. Pressure was applied at 1 kgf / cm ² (98.0665 KPa) with a dispenser coating apparatus ML505X manufactured by MUSASHI Engineering, and a 5 cm long line was applied onto a silicon wafer at 10 mm / sec with SHOTMASTER 3 to form a coating film. The silicon wafer substrate on which the coating film was formed was dried on a hot plate at 80 ° C. for 10 minutes and then heated in an oven at 230 ° C. for 30 minutes to obtain a polyimide film (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.
Table 1 shows the viscosity of the thermosetting composition (1) and the line width and film pressure of the polyimide film (insulating film) obtained from the thermosetting composition (1). The line had a sufficient thickness.

<Insulation test>
1 mL of the thermosetting composition (1) was applied on a chromium substrate, a thin film was formed by spin coating, dried on a hot plate at 80 ° C. for 5 minutes, and cured in an oven at 230 ° C. for 30 minutes. Then, aluminum was vapor-deposited on the polyimide resin film, and the electrode was created. Table 2 shows the results of measuring the dielectric constant, dielectric loss tangent, volume resistivity, withstand voltage, and dielectric strength of the obtained polyimide insulating film.

[Example 2] Thermosetting composition (2)
A 500 ml three-necked flask equipped with a stirrer and a raw material charging inlet was charged with raw materials as shown below and stirred at 60 ° C. for 1 hour under a dry nitrogen stream. Got.

The raw materials were charged 77.0 g of BANIX and 33.0 g of GBL.
The raw materials were added to 110 g of the light brown alkenyl-substituted nadiimide 70% by weight solution obtained as described above, and the mixture was further stirred for 3 hours at room temperature under a dry nitrogen stream. As a result, brown polyamic acid was formed, A mixed solution was made. Let the obtained solution be a thermosetting composition (2). The viscosity of this composition was 6,000 mPa · s (25 ° C.). The weight average molecular weight measured by GPC of the polyamic acid was 34,820.

The raw materials were charged with ODPA 14.0 g, BAP 18.9 g, MA 0.2 g and GBL 77.0 g.
About the thermosetting composition (2), it carried out similarly to Example 1, and performed the coating property test and the insulation test. Table 1 shows the results of the coatability test, and Table 2 shows the results of the insulation test. The line had a sufficient thickness.

[Example 3] Thermosetting composition (3)
A light brown alkenyl-substituted nadiimide 70% by weight solution was obtained in the same manner as in Example 2 except that BANIM was used as the alkenyl-substituted nadiimide (C).

  The raw materials were added to 110 g of the light brown alkenyl-substituted nadiimide 70% by weight solution obtained as described above, and the mixture was stirred at room temperature for 3 hours under a dry nitrogen stream to produce brown polyamic acid. A mixed solution was made. Let the obtained solution be a thermosetting composition (3). The viscosity of this composition was 7,900 mPa · s (25 ° C.). The weight average molecular weight measured by GPC of the polyamic acid was 45,240.

The raw materials were charged with ODPA 14.0 g, BAP 18.9 g, MA 0.2 g and GBL 77.0 g.
About the thermosetting composition (3), the coating property test and the insulation test were done like Example 1. FIG. Table 1 shows the results of the coatability test, and Table 2 shows the results of the insulation test. The line had a sufficient thickness.

[Example 4] Thermosetting composition (4)
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 at room temperature for 3 hours under a dry nitrogen stream to obtain a brown polyamic acid 30% by weight solution. . The viscosity of this solution was 13,000 mPa · s (25 ° C.). The weight average molecular weight measured by GPC was 30,840.

The raw materials were ODPA 13.7 g, BAP 18.9 g, CA 0.4 g and GBL 77.0
g was charged.
110 g of the 30% by weight brown polyamic acid solution obtained above and 110 g of the 70% by weight alkenyl-substituted nadiimide solution obtained by the same method as in Example 1 were mixed to obtain a thermosetting composition (4). The viscosity of this composition was 4,900 mPa · s (25 ° C.).

About the thermosetting composition (4), it carried out similarly to Example 1, and performed the coating property test and the insulation test. Table 1 shows the results of the coatability test, and Table 2 shows the results of the insulation test. The line had a sufficient thickness.
[Comparative Example 1] Thermosetting composition (6)
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 under a dry nitrogen stream to obtain a 12% by weight solution of polyamic acid. This solution was designated as a thermosetting composition (6). The viscosity of this composition was 3100 mPa · s.

The raw materials were charged with 15.5 g of ODPA, 20.5 g of BAP, 132.0 g of EDM, and 132.0 g of GBL.
About the thermosetting composition (6), it carried out similarly to Example 1, and performed the coating property test and the viscosity measurement. The results are shown in Table 1. Although the viscosity of the thermosetting composition (6) was appropriate as a thermosetting composition for a dispenser, it does not contain alkenyl-substituted nadiimide (C), and the solid content concentration in the composition is small. The line did not have sufficient thickness.

[Comparative Example 2] Thermosetting composition (7)
A 500 ml three-necked flask equipped with a stirrer and a raw material charging inlet was charged with raw materials as shown below and stirred at 60 ° C. for 1 hour under a dry nitrogen stream. Got. Let the obtained solution be a thermosetting composition (7). The viscosity of this composition was 660 mPa · s. A film was produced under the same conditions as in the coating property test of Example 1 except that the thermosetting composition (7) was used. The film was brittle and a polyimide insulating film could not be obtained.

The raw materials were charged 77.0 g of BANIX and 33.0 g of GBL.
[Comparative Example 3] Thermosetting composition (8)
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 at room temperature for 3 hours under a dry nitrogen stream. A polyamic acid solution was obtained by precipitation of low molecular components. I couldn't.

The raw materials were charged with 10.2 g of ODPA, 16.3 g of DDS, 6.5 g of MA and 77.0 g of GBL.
The precipitate was dissolved in NMP, and the weight average molecular weight measured by GPC was 980.

  As is clear from Table 2, it was found that the obtained polyimide insulating film was excellent in withstand voltage. It has been found that the compounds of the present invention are also excellent in terms of electrical properties.

  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 (29)

Alkenyl-substituted nadiimide (C),
And a thermosetting composition for forming an insulating film, comprising a polyamic acid (B) having a weight average molecular weight of 25,000 to 50,000 having a structural unit represented by the following formula (2), and having a viscosity of 400 to 50,000 mPa · s. Product (however, it does not contain quinonediazide compound).

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.)   2. The thermosetting composition for forming an insulating film according to claim 1, wherein the polyamic acid (B) is contained in an amount of 0.01 to 50 wt% when the entire thermosetting composition is 100 wt%. .   The thermosetting composition for insulating film formation of Claim 1 or 2 used for dispenser application | coating. The polyamic acid (B) is a polyamic acid having at least one molecular end group selected from the group consisting of a group represented by the following formula (21) and a group represented by the following formula (22). Item 4. The thermosetting composition for forming an insulating film according to any one of Items 1 to 3.

(In formula (21), R ⁵ is an organic group having 2 to 100 carbon atoms, and in formula (22), R ⁶ is an organic group having 2 to 100 carbon atoms.) The polyamic acid (B) is represented by the following formula (11), at least one monomer selected from the group consisting of a compound represented by the following formula (13) and a compound represented by the following formula (14). The thermosetting composition for forming an insulating film according to claim 1, which is a polyamic acid obtained by copolymerizing a compound represented by formula (12) below and a compound represented by the following formula (12).

(In the formula (11), R ³ is an organic group having 2 to 100 carbon atoms, in the formula (12), R ⁴ is an organic group having 2 to 100 carbon atoms, and in the formula (13), R ⁶ is an organic group of 2 to 100 carbon atoms, in the formula (14), R ⁵ is an organic group having 2-100 carbon atoms.) Alkenyl-substituted nadiimide (C),
And a thermosetting composition comprising a polyamic acid (B) having a structural unit represented by the following formula (2):
The polyamic acid (B) is at least one molecular end selected from the group consisting of a group represented by the following formula (23), a group represented by the following formula (24), and a group represented by the following formula (25) A thermosetting composition for forming an insulating film having a viscosity of 400 to 50000 mPa · s, which is a polyamic acid having a group (however, a quinonediazide compound is not included).

(In formula (2), R ³ and R ⁴ are each independently an organic group having 2 to 100 carbon atoms.) Alkenyl-substituted nadiimide (C),
And a thermosetting composition comprising a polyamic acid (B) having a structural unit represented by the following formula (2):
The polyamic acid (B) is at least one compound selected from the group consisting of maleic anhydride and citraconic anhydride, a compound represented by the following formula (11), and a compound represented by the following formula (12) A thermosetting composition for forming an insulating film having a viscosity of 400 to 50000 mPa · s, which is a polyamic acid obtained by copolymerizing (not including a quinonediazide compound).

(In Formula (2) and Formula (11), R ³ is an organic group having 2 to 100 carbon atoms, and in Formula (2) and Formula (12), R ⁴ is an organic group having 2 to 100 carbon atoms. .) The said alkenyl substituted nadiimide (C) is a compound represented by following formula (5), The thermosetting composition for insulating film formation in any one of Claims 1-7.

(In formula (5), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl of 3 to 6 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, 6 to 12 carbon atoms Either aryl or benzyl, n is 1 or 2,
When n = 1, Q is hydrogen, hydroxyl group, alkyl having 1 to 12 carbon atoms, alkenyl having 1 to 3 carbon atoms, hydroxyalkyl having 1 to 12 carbon atoms, hydroxyalkenyl having 2 to 12 carbon atoms, or 5 to 5 carbon atoms. Cycloalkyl having 8 carbon atoms, hydroxycycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, — [(C _q H _2q ) O _t (C _r H _2r O) _u C _s H _2s X] A group represented by the formula (wherein q, r, and s are each independently an integer of 2 to 6, t is 0 or 1, u is an integer of 0 to 30, and X is hydrogen or a hydroxyl group),-( R) _a group represented by _a- C ₆ H ₄ -R ⁴¹ (where a is 0 or 1, R is alkylene having 1 to 4 carbon atoms, R ⁴¹ is hydrogen or alkyl having 1 to 4 carbon atoms) _{), - C 6 H 4 -T} -C 6 H 5 , a group represented by the table in _{-C 6 H 4 -T-C 6} H 4 -OH Group (wherein, T is _{-CH 2 -, - C (CH} 3) 2 -, isopropylidene, -CO -, - S- or -SO ₂ - in which), or their groups containing an aromatic ring In the case, 1 to 3 hydrogen atoms directly bonded to the aromatic ring are groups substituted with a hydroxyl group,
When n = 2, Q is alkylene having 2 to 20 carbons, cycloalkylene having 5 to 8 carbons,-[(C _q H _2q O) _t (C _r H _2r O) _u C _s H _2s ]- A group represented by the formula (wherein q, r and s are each independently an integer of 2 to 6, t is 0 or 1, u is an integer of 1 to 30), an arylene having 6 to 12 carbon atoms,-( R) _a group represented by _a —C ₆ H ₄ —R ⁵¹ — (wherein, a is 0 or 1, R and R ⁵¹ each independently represent alkylene having 1 to 8 carbons, or cyclohexane having 1 to 8 carbons) A group represented by —C ₆ H ₄ —TC ₆ H ₄ — (wherein T represents —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —O—). , —OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ O—, —S—, —SO ₂ —), or when these groups contain an aromatic ring, 3 hydrogens Is a group that has been replaced by a hydroxyl group. )   The thermosetting composition for forming an insulating film according to claim 8, wherein n is 2 in the formula (5). In the formula (5), n is 2, Q is alkylene having 2 to 10 carbon atoms, and a group represented by-(R) _a -C ₆ H ₄ -R ^51- (wherein, a is 0 or 1, R and R ⁵¹ are each independently alkylene having 1 to 4 carbon atoms, or a group represented by —C ₆ H ₄ —TC ₆ H ₄ — (wherein T is —CH ₂ — , —C (CH ₃ ) ₂ —, —CO—, —O—, —OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ O—, —S—, —SO ₂ —). Item 9. The thermosetting composition for forming an insulating film according to Item 8. In the formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, Q is represented by-(CH ₂ ) _6- , and the formula (6). The thermosetting composition for forming an insulating film according to claim 8, which is a group represented by formula (7) or a group represented by formula (7):

  The alkenyl-substituted nadiimide compound (C) includes at least one compound in which n is 1 in the formula (5) and at least one compound in which n is 2 in the formula (5). The thermosetting composition for insulating film formation of description. In the formula (5), n is 1 in the alkenyl-substituted nadiimide compound (C), Q is alkyl 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 + 1] a group represented by (in this case, q, r, s are each independently an integer from 2 to 6, t Is 0 or 1, u is an integer of 1 to 30), a group represented by-(R) _a -C ₆ H ₄ -R ⁴¹ (where a is 0 or 1, R is 1 to 4 alkylene, R ⁴¹ represents hydrogen or alkyl having 1 to 4 carbon atoms), or a group represented by —C ₆ H ₄ —TC ₆ H ₅ (wherein T is —CH ₂ —, — At least one compound which is C (CH ₃ ) ₂ —, —CO—, —S— or —SO ₂ —;
The thermosetting composition for forming an insulating film according to claim 8, comprising at least one compound in which n is 2 in the formula (5). In the alkenyl-substituted nadiimide compound (C), in Formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 1, and Q is 1 to 12 carbons. At least one compound that is alkyl, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, or benzyl;
The thermosetting composition for forming an insulating film according to claim 8, comprising at least one compound in which n is 2 in the formula (5). In the alkenyl-substituted nadiimide compound (C), in Formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbons, n is 1, and Q is 1 to 12 carbons. At least one compound which is alkyl or aryl having 6 to 12 carbon atoms;
In the formula (5), R ¹ and R ² are each independently hydrogen or alkyl having 1 to 6 carbon atoms, n is 2, Q is represented by-(CH ₂ ) _6- , and the formula (6). The insulating film-forming thermosetting composition according to claim 8, comprising at least one compound that is a group represented by formula (7) or a group represented by formula (7):

  The thermosetting composition for forming an insulating film according to any one of claims 1 to 15, further comprising a solvent (D).   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 for insulating film formation according to claim 16, which is at least one solvent selected from the group consisting of glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone and γ-butyrolactone. Sex composition.   The polyimide film obtained by apply | coating the thermosetting composition for insulating film formation in any one of Claims 1-17 on a board | substrate, forming a coating film, and hardening-treating this coating film.   The polyimide film according to claim 18, wherein the application is performed by a dispenser application method.   The polyimide film according to claim 18, wherein the polyimide film is a patterned polyimide film.   The process of apply | coating the thermosetting composition for insulating film formation in any one of Claims 1-17 on a board | substrate, and forming a coating film, and the process of forming a polyimide film by hardening | curing this coating film The manufacturing method of the polyimide film containing this.   The method for producing a polyimide film according to claim 21, wherein the coating is performed by a dispenser coating method.   The method for producing a polyimide film according to claim 21 or 22, wherein the polyimide film is a patterned polyimide film.   A film substrate comprising the polyimide film according to claim 18.   An electronic component having the film substrate according to claim 24.   A silicon wafer substrate having the polyimide film according to claim 18.   An electronic component comprising the silicon wafer substrate according to claim 26. In the presence of alkenyl-substituted nadiimide (C) and solvent (D), at least one monomer selected from the group consisting of a compound represented by the following formula (13) and a compound represented by the following formula (14), 11) and a compound represented by the following formula (12) are copolymerized,
It has a structural unit represented by alkenyl-substituted nadiimide (C) and the following formula (2), has a weight average molecular weight of 25,000 to 50,000, a group represented by the following formula (21) and the following formula (22 A thermosetting composition having a viscosity of 400 to 50000 mPa · s (including a quinonediazide compound), comprising a polyamic acid (B) having at least one molecular end group selected from the group consisting of groups represented by: Method of manufacturing).

(In the formulas (2) and (11), R ³ is an organic group having 2 to 100 carbon atoms. In the formulas (2) and (12), R ⁴ is an organic group having 2 to 100 carbon atoms. (In (13) and (22), R ⁶ is an organic group having 2 to 100 carbon atoms, and in formulas (14) and (21), R ⁵ is an organic group having 2 to 100 carbon atoms.) In the presence of alkenyl-substituted nadiimide (C) and solvent (D), at least one compound selected from the group consisting of maleic anhydride and citraconic anhydride, a compound represented by the following formula (11) and a following formula (12) A compound represented by the formula:
An alkenyl-substituted nadiimide (C) and a structural unit represented by the following formula (2), a group represented by the following formula (23), a group represented by the following formula (24), and a formula (25) A thermosetting composition having a viscosity of 400 to 50000 mPa · s, including a polyamic acid (B) having at least one molecular end group selected from the group consisting of the groups represented (however, excluding a quinonediazide compound) How to manufacture.

(In formulas (2) and (11), R ³ is an organic group having 2 to 100 carbon atoms, and in formulas (2) and (12), R ⁴ is an organic group having 2 to 100 carbon atoms.)