TW201636394A - Heat-curable resin composition - Google Patents

Abstract

The present invention provides a heat-curable resin composition comprising: (A) a polyimide resin having a structure represented by formula (1-a) and a structure represented by formula (1-b); and (B) at least one heat-curable resin selected from an epoxy resin, a bismaleimide resin, a cyanate ester resin, a bisallylnadic imide resin, a vinylbenzyl ether resin, a benzooxazine resin and a polymerization product of a bismaleimide with a diamine (in the formulae, the groups are as defined in the description).

Description

Thermosetting resin composition

The present invention relates to a thermosetting resin composition useful for forming an insulating layer of a circuit board such as a coreless circuit board, a flexible circuit board, or a wafer level wafer size package.

An insulating layer used for a circuit board such as a coreless circuit board, a flexible circuit board, or a wafer level wafer size package requires a low coefficient of thermal expansion (CTE) and low elasticity in order to suppress substrate warpage. rate. As an insulating resin material for forming the insulating layer, Patent Document 1 discloses a resin composition containing an expansion-releasing component made of an acrylic resin having solubility in an organic solvent. However, the insulating layer formed of the conventional insulating resin material has a problem that the water repellency is high and the ink having high hydrophilicity is repelled.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2014/132654

The present invention has been made in view of the above, and an object thereof is to provide a thermosetting resin composition which can form an insulating layer having high hydrophilicity.

In order to solve the problem, the inventors of the present invention have repeatedly conducted an active review and found that a thermosetting resin composition having a specific structure and a thermosetting resin composition such as an epoxy resin can be used to form an insulating layer having high hydrophilicity. Based on this finding, the present invention is as follows.

[1] A thermosetting resin composition comprising (A) a polyimine resin having a structure represented by formula (1-a) and a structure represented by formula (1-b),

Wherein R1 represents a residue after removing a hydroxyl group of a polycarbonate diol, R2 represents a residue after removing a carboxyl group or an acid anhydride group of a polybasic acid or an acid anhydride thereof, and R3 represents a residue after removing an isocyanate group of a diisocyanate compound; ], and (B) from epoxy resin, bismaleimide resin, cyanate resin, More than one type of thermosetting selected from the group consisting of bisallylnadic imide resin, vinyl benzyl ether resin, benzoxazine resin, and polymer of bismaleimide and diamine Resin.

[2] The thermosetting resin composition according to the above [1], wherein the polyimine resin of the component (A) has a structure represented by the formula (abc):

[wherein, R1 to R3 are as described in the above [1], and n and m represent integers].

[3] The thermosetting resin composition according to the above [1] or [2] wherein the polycarbonate diol has a number average molecular weight of 500 to 5,000.

[4] The thermosetting resin composition according to the above [1] or [2] wherein the polycarbonate diol has a number average molecular weight of 1,000 to 3,000.

[5] The thermosetting resin composition according to any one of [1] to [4] wherein R1 is a divalent group represented by the formula (1-c):

[wherein, k+1 R4 each independently represent an alkylene group having 1 to 20 carbon atoms which may have a substituent, and k represents an integer of 5 to 30].

[6] The thermosetting resin composition according to the above [5], wherein each of k+1 R4 is independently an alkylene group having 1 to 20 carbon atoms.

[7] The thermosetting resin composition according to the above [5], wherein each of k+1 R4 is independently an alkylene group having 2 to 18 carbon atoms.

[8] The thermosetting resin composition according to the above [5], wherein each of k+1 R4 is independently an alkylene group having 3 to 16 carbon atoms.

[9] The thermosetting resin composition according to any one of [5] to [8] wherein k is an integer of 5 to 25.

[10] The thermosetting resin composition according to any one of [5] to [8] wherein k is an integer of from 5 to 20.

[1] The thermosetting resin composition according to any one of the above [1], wherein R2 represents one or more selected from the group consisting of a tetravalent group represented by any one of the following formulas:

Wherein A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(CCl ₃ ) ₂ , In the above, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms].

[12] The thermosetting resin composition according to any one of [1] to [10] wherein R2 represents a tetravalent group represented by the following formula:

Wherein A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(CCl ₃ ) ₂ , In the above, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms].

[13] The thermosetting resin composition according to the above [11] or [12] wherein, in the above formula, A is an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C (CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(CCl ₃ ) ₂ , and the hydrogen atom bonded to the carbon atom is unsubstituted.

[14] The thermosetting resin composition according to the above [11] or [12] wherein, in the above formula, A is CO, and a hydrogen atom bonded to a carbon atom is unsubstituted.

[15] The thermosetting resin composition according to any one of the above [1], wherein R3 represents one or more selected from the group consisting of a divalent group represented by any one of the following formulas:

[In the formula, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms].

[16] The thermosetting resin composition according to the above [15], wherein the substituent selected from the halogen atom and the alkyl group having 1 to 8 carbon atoms is an alkyl group having 1 to 8 carbon atoms.

The thermosetting resin composition of any one of the above-mentioned [1] to [14], wherein R3 represents one or more selected from the group consisting of a divalent group represented by any one of the following formulas:

[In the formula, a hydrogen atom bonded to a carbon atom may be substituted with an alkyl group having 1 to 8 carbon atoms].

[18] The thermosetting resin composition according to any one of [15] to [17] wherein the alkyl group having 1 to 8 carbon atoms is an alkyl group having 1 to 6 carbon atoms.

[19] The thermosetting resin composition according to any one of [15] to [17] wherein the alkyl group having 1 to 8 carbon atoms is a methyl group.

[20] The thermosetting resin composition according to any one of [1] to [14] wherein R3 is 4-methyl-1,3-phenylene.

[21] The thermosetting resin composition according to any one of [1] to [20] wherein the polyamidene resin of the component (A) has a number average molecular weight of 5,000 to 25,000.

[22] The thermosetting resin composition according to any one of [1] to [20] wherein the polyamidene resin of the component (A) has a number average molecular weight of 5,000 to 20,000.

[23] The thermosetting resin composition according to any one of [1] to [22] wherein the glass transition temperature of the polyimine resin of the component (A) is 30 ° C or lower.

[24] The thermosetting resin composition according to any one of [1] to [22] wherein the glass transition temperature of the polyimine resin of the component (A) is -15 ° C to 29 ° C.

[25] The thermosetting resin composition according to any one of [1] to [22] wherein the glass transition temperature of the polyimine resin of the component (A) is -10 ° C to 20 ° C.

[26] The thermosetting resin composition according to any one of [1] to [25] wherein the thermosetting resin of the component (B) is an epoxy resin.

[27] The thermosetting resin composition according to [26] above, wherein the epoxy resin has an epoxy equivalent of from 90 to 500.

[28] The thermosetting resin composition according to [26] above, wherein the epoxy tree The epoxy equivalent of the fat is 90~300.

[29] The thermosetting resin composition according to [26] above, wherein the epoxy resin has an epoxy equivalent of from 110 to 250.

[30] The thermosetting resin composition according to any one of [26] to [29] wherein the epoxy resin is a liquid epoxy resin.

[31] The thermosetting resin composition according to any one of [1] to [30] wherein the content of the thermosetting resin of the component (B) is relative to the polyamidene resin 100 of the component (A). The parts by weight are 15 to 80 parts by weight.

[32] The thermosetting resin composition according to any one of [1] to [30] wherein the content of the thermosetting resin of the component (B) is relative to the polyimine resin 100 of the component (A). The parts by weight are 30 to 80 parts by weight.

[33] The thermosetting resin composition according to any one of [1] to [30] wherein the content of the thermosetting resin of the component (B) is relative to the polyimine resin 100 of the component (A). The parts by weight are 40 to 70 parts by weight.

[34] The thermosetting resin composition according to any one of [1] to [33] further comprising an inorganic filler.

[35] The thermosetting resin composition according to [34] above, wherein the inorganic filler is cerium oxide.

[36] The thermosetting resin composition according to the above [34] or [35] wherein the content of the inorganic filler is 50 to 95% by weight based on the nonvolatile content of the thermosetting resin composition.

[37] The thermosetting resin composition according to the above [34] or [35] wherein the content of the inorganic filler is 60 to 93% by weight based on the nonvolatile content of the thermosetting resin composition.

[38] The thermosetting resin composition according to the above [34] or [35] wherein the content of the inorganic filler is 70 to 90% by weight based on the nonvolatile content of the thermosetting resin composition.

[39] The thermosetting resin composition according to the above [34] or [35] wherein the content of the inorganic filler is from 80 to 85% by weight based on the nonvolatile content of the thermosetting resin composition.

[40] The thermosetting resin composition according to any one of [1] to [39] further comprising a curing accelerator.

[41] The thermosetting resin composition according to the above [40], wherein the content of the curing accelerator is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the thermosetting resin of the component (B).

[42] The thermosetting resin composition according to the above [40], wherein the content of the curing accelerator is preferably from 1 to 3 parts by weight based on 100 parts by weight of the thermosetting resin of the component (B).

[43] A film comprising a layer formed of the thermosetting resin composition according to any one of the above [1] to [42].

[44] A printed wiring board having a cured product formed of the thermosetting resin composition according to any one of the above [1] to [42] as an insulating layer.

[45] A wafer-level wafer-size package having a cured product formed of the thermosetting resin composition according to any one of the above [1] to [42] as an insulating layer.

The thermosetting resin composition of the present invention can form an insulating layer having high hydrophilicity. Such a hydrophilic high insulating layer can uniformly apply a highly hydrophilic ink, and is useful for a circuit board such as a wafer level wafer size package.

The thermosetting resin composition of the present invention is characterized by comprising a structure having a structure derived from a polycarbonate diol, a structure derived from a diisocyanate compound, and a polyanthracene derived from a polybasic acid or an anhydride thereof. Imine resin (ingredient (A)), and self-epoxy resin, bismaleimide resin, cyanate resin, bisallyl nadic amide resin, vinyl benzyl ether resin, benzoxazole One or more kinds of thermosetting resins (component (B)) selected from the group consisting of a sulfonate resin and a polymer of bismaleimide and diamine. Hereinafter, the order will be described.

<(A) Polyimine Resin]

The component (A) has a structure represented by the formula (1-a) (a urethane and carbonate structure, hereinafter sometimes referred to simply as "structure (1-a)"), and is represented by the formula (1-b) The structure (the quinone imine structure, hereinafter sometimes referred to simply as "structure (1-b)") is a polyimine resin.

Wherein R1 represents a residue after removing a hydroxyl group of a polycarbonate diol, R2 represents a residue after removing a carboxyl group or an acid anhydride group of a polybasic acid or an acid anhydride thereof, and R3 represents a residue after removing an isocyanate group of a diisocyanate compound; ].

Further, the end of the above chemical formula is not a methyl group but a bonding position. The same is true for other chemical formulas.

The polyimine resin of the component (A) can be produced by using (a) a polycarbonate diol (hereinafter sometimes referred to as "raw material (a)")) and (b) a diisocyanate compound (hereinafter referred to as In the case, it is described as "raw material (b)"), and (c) polybasic acid or its acid anhydride (hereinafter referred to as "raw material (c)"). The component (A) may be used alone or in combination of two or more. In addition, one type of the raw materials (a) to (c) may be used alone or two or more types may be used in combination.

The number average molecular weight of the polycarbonate diol of the raw material (a) is preferably from 500 to 5,000, more preferably from 500 to 5,000, from the viewpoint of the flexibility of the cured product of the resin composition and the solvent solubility of the component (A). 1,000~3,000.

Further, in the present invention, the number average molecular weight is a value measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). By using the number average molecular weight of the GPC method, for example, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. can be used. As a column, chloroform was used as a mobile phase, and the measurement was performed at a column temperature of 40 ° C, and was calculated using a calibration line of standard polystyrene.

The hydroxyl equivalent of the polycarbonate diol is preferably from 250 to 1,250, more preferably from 500 to 1,000, from the viewpoint of the flexibility of the cured product of the resin composition and the viewpoint of chemical resistance.

A commercially available product can be used as the polycarbonate diol. Such commercially available products are, for example, C-1015N, C-2015N manufactured by KURARAY Co., Ltd., T-6002, T-4672, T-5652, manufactured by Asahi Kasei Chemical Co., Ltd., CD205, CD205PL manufactured by DAICEL Co., Ltd. , CD205HL, CD210, CD210PL, NIPPOLAN 981, 980R, etc. made by Japan POLYURETHANE Industrial Co., Ltd.

The diisocyanate compound as the raw material (b) is exemplified by an aromatic diisocyanate such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene diisocyanate or diphenylmethane diisocyanate; An aliphatic diisocyanate such as methyl diisocyanate; an alicyclic diisocyanate such as isophorone diisocyanate. Among these, an aromatic diisocyanate is preferred, and toluene-2,4-diisocyanate is more preferred.

The polybasic acid or the acid anhydride thereof as the raw material (c) is exemplified by, for example, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5- Quaternary (2,5-dioxotetrahydrofuranyl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid Acid and the anhydrides thereof, tribasic acids such as trimellitic acid, cyclohexanetricarboxylic acid and the like, and the anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro- 2,5-dioxo-3-furanyl)-naphthalene (1,2-C)furan-1,3-dione or the like. Among these, a tetrabasic acid anhydride is preferred, a tetrabasic acid dianhydride is more preferred, and a benzophenone tetracarboxylic dianhydride is more preferred.

R1 is preferably a divalent group represented by the formula (1-c):

[wherein, k+1 R4 each independently represent an alkylene group having 1 to 20 carbon atoms which may have a substituent, and k represents an integer of 5 to 30].

The alkyl group of R4 may be linear or branched. The alkylene group of R4 may have a substituent such as a halogen atom, a cycloalkyl group having 4 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. The alkylene group of R4 is preferably unsubstituted.

The halogen atom is exemplified by, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The cycloalkyl group having 4 to 8 carbon atoms is exemplified by, for example, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group.

Examples of the aryl group having 6 to 14 carbon atoms are, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, and a 9-fluorenyl group.

The k+1 R4 groups are each independently preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 2 to 18 carbon atoms, and more preferably an alkylene group having 3 to 16 carbon atoms. k is preferably an integer from 5 to 25, more preferably an integer from 5 to 20.

R2 is preferably one or more selected from the group consisting of four valent groups represented by any one of the following formulas:

Wherein A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(CCl ₃ ) ₂ , In the above, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms].

R2 (tetravalent group) represented by the above formula is preferably a tetravalent group having an aromatic ring, more preferably a tetravalent group having two or more aromatic rings, and most preferably a tetravalent group represented by the following formula:

Wherein A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(CCl ₃ ) ₂ , In the above, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms].

A is preferably CO.

The hydrogen atom bonded to a carbon atom in the above formula (i.e., a hydrogen atom bonded to a carbon atom in a tetravalent group of R2) may also be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms. . The hydrogen atom is preferably unsubstituted.

The halogen atom is exemplified by the above.

The alkyl group may be a straight chain or a branched chain. Examples of the alkyl group having 1 to 8 carbon atoms are, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group, and a new one. Pentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl Base, heptyl, octyl.

R3 is preferably one or more selected from the group consisting of a divalent group represented by any one of the following formulas:

[In the formula, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms]. Further, the end of the above formula is not a methyl group but a bonding position. For example, the last formula is not octane, but represents hexamethylene.

The hydrogen atom bonded to a carbon atom in the above formula (that is, a hydrogen atom bonded to a carbon atom in a divalent group of R3) may also be a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms ( It is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.

Examples of the halogen atom and the alkyl group having 1 to 8 carbon atoms are as described above. Examples of the alkyl group having 1 to 6 carbon atoms are, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, an isopentyl group, and a new group. Pentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl base.

In the R3 (divalent group) represented by the above formula, a divalent group having an aromatic ring or an alicyclic ring is preferred, and a divalent organic group having an alicyclic ring is more preferred. When having a divalent group of an aromatic ring, it is preferably a divalent group represented by any one of the following formulae:

[wherein, a hydrogen atom bonded to a carbon atom may be substituted by an alkyl group having 1 to 8 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group)], preferably a 4-methyl group. -1,3-phenylene (i.e., the residue of the isocyanate group removed by toluene-2,4-diisocyanate).

The number average molecular weight of the polyimine resin of the component (A) is preferably 5,000 or more, more preferably 7,000 or more, more preferably 7,000 or more, based on the resin composition and the mixture of the component (A) and the resin composition. 9,000 or more, preferably 25,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less.

The glass transition temperature of the polyimine resin of the component (A) is preferably 30 ° C or less, more preferably -15 ° C to 29 ° C, and more preferably from the viewpoint of imparting sufficient flexibility to the cured product of the resin composition. -10 ° C ~ 20 ° C. Here, the glass transition temperature of the polyimide resin may be a peak temperature of tan δ obtained by dynamic viscoelasticity measurement, or may be read from a thermomechanical analysis by a thermomechanical analysis device by a tensile load method.

The polyimine resin of the component (A) can be produced, for example, as follows. First, the ratio of the amount of the isocyanate group of the polycarbonate diol of the raw material (a) and the diisocyanate compound of the raw material (b) to the hydroxyl group of the polycarbonate diol and the amount of the isocyanate group of the diisocyanate compound exceeds 1 mole. The reaction is carried out to produce an isocyanate reactant represented by the formula (ab) (hereinafter sometimes simply referred to as "diisocyanate reactant (ab)"),

[wherein, R1 and R3 are synonymous with the above, and n represents an integer]. n is, for example, an integer of 1 to 100, preferably an integer of 1 to 10.

Preferably, the reaction is carried out such that the hydroxyl group of the polycarbonate diol of the starting material (a): the molar ratio of the isocyanate group of the diisocyanate compound of the starting material (b) is 1:1.5 to 1:2.5.

The reaction of the polycarbonate diol of the raw material (a) with the diisocyanate compound of the raw material (b) is usually carried out in an organic solvent at a temperature of 80 ° C or lower for 1 to 8 hours. The reaction may also use a catalyst as needed.

As the above organic solvent, for example, N,N'-dimethylformamide, N,N'-diethylformamide, N,N'-dimethylacetamide, N,N'-di can be exemplified. Ethyl acetamide, dimethyl hydrazine, diethyl hydrazine, N-methyl-2-pyrrolidone, tetramethyl urea, γ-butyrolactone, cyclohexanone, diethylene glycol A polar solvent such as diglyme, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate. These polar solvents may be used alone or in combination of two or more. Further, if necessary, a nonpolar solvent such as an aromatic hydrocarbon may be appropriately mixed and used.

As a solvent, for example, dibutyltin dilaurate, two An organometallic catalyst such as dimethyltin chloride, cobalt naphthenate or zinc naphthenate.

Next, the polybasic acid of the starting material (c) or its anhydride is reacted with the obtained diisocyanate reactant (ab). The reaction ratio of the polybasic acid or its anhydride is not particularly limited, but in order to prevent the isocyanate group from remaining in the polyimine resin of the component (A), the amount of the isocyanate group contained in the raw material (b) is set. In the case of X, the molar amount of the hydroxyl group contained in the raw material (a) is W, and the molar amount of the carboxyl group contained in the raw material (c) is Y ₁ and the molar amount of the acid anhydride group is set to Y _{2 .} In the case, it is preferred to carry out the reaction in an amount satisfying the relationship of 0.5Y ₁ + Y ₂ > XW ≧ (0.5Y ₁ + Y ₂ )/5.

The reaction of the diisocyanate reactant (a-b) with the polybasic acid of the starting material (c) or its anhydride is usually carried out at a temperature of from 120 to 180 ° C for 2 to 24 hours. The reaction may also use a catalyst as needed. Further, the reaction may be carried out by further adding the above organic solvent.

As the above catalyst, for example, tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, N,N'-dimethylpiperidine, α-methylbenzyldimethyl group are exemplified. Amines such as amines, N-methylmorpholine, and triethylenediamine. Of these, it is preferably triethylenediamine.

As described above, the polyimine resin of the component (A) can be produced. As the component (A), it is more preferably a polyimine resin having a structure represented by the formula (abc):

[wherein, R1 to R3 are synonymous with the above, and n and m represent an integer]. n is, for example, an integer of 1 to 100, preferably an integer of 1 to 10, and m is an integer of, for example, 1 to 100, preferably an integer of 1 to 10.

In order to prevent the isocyanate group (-NCO) from remaining as much as possible in the polyimine resin of the component (A), it is preferred to confirm the disappearance of the isocyanate group by FT-IR or the like in the above reaction. The end of the polyimine resin thus obtained may be represented by the formula (1-d) or the formula (1-e):

[In the formula, R2 is synonymous with the above].

In the production of the polyimine resin of the component (A), after the diisocyanate reactant (ab) is reacted with the polybasic acid of the starting material (c) or an anhydride thereof, the obtained reactant is further reacted with a diisocyanate compound to produce a higher molecular weight. Polyimine resin. The reaction ratio of the isocyanate compound in this case is not particularly limited, but the molar amount of the isocyanate group contained in the raw material (b) is X, and the molar amount of the hydroxyl group contained in the raw material (a) is set to W, the molar amount of the carboxyl group contained in the raw material (c) is Y ₁ and the molar amount of the acid anhydride group is Y ₂ , and the molar amount of the isocyanate group contained in the further reacted diisocyanate compound is set. In the case of Z, it is preferred to carry out the reaction in an amount satisfying the relationship of (0.5Y ₁ + Y ₂ ) - (XW) > Z ≧ 0.

Further, the above reaction with the diisocyanate compound is usually carried out at a temperature of from 120 to 180 ° C for 2 to 24 hours.

In order to remove insoluble matter from the solution containing the polyimine resin, it may be filtered as needed. Thus, the polyimine resin of the component (A) can be obtained in the form of a varnish. The amount of the solvent in the polyimide varnish can be appropriately adjusted by appropriately adjusting the amount of the solvent at the time of the reaction or adding or removing the solvent after the reaction.

The acid value of the polyimine resin is preferably from 3 to 30 mgKOH/g, preferably from 5 to 20 mg KOH/g. The viscosity of the polyimide resin is preferably from 3 to 15 Pa at 50% by weight of the solid component. s, better 5~10Pa. s.

<(B) Thermosetting resin>

Ingredient (B) is derived from epoxy resin, bismaleimide resin, cyanate resin, bisallyl nadic ylidene imide resin, vinyl benzyl ether resin, benzoxazine resin, and double horse One or more types of thermosetting resins selected from the group consisting of polymers of imine and diamine. Only one of these may be used, or two or more types may be used in combination.

The epoxy resin in the present invention means two in one molecule The above thermosetting resin having an epoxy group and an epoxy group equivalent of 80 to 8,000. The epoxy resin may be used alone or in combination of two or more. Further, a phenoxy resin having an epoxy group similarly to an epoxy resin means a thermoplastic resin having an epoxy equivalent of more than 8,000 in the present invention, and is distinguished from an epoxy resin. The epoxy equivalent of the epoxy resin is preferably from 90 to 500, more preferably from 90 to 300, and even more preferably from 110 to 250.

Examples of the epoxy resin are, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, and third butyl Base catechol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type Epoxy resin, bismuth epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin with spiral ring, Cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. Preferably, the epoxy resin having an aromatic ring is at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin and naphthalene epoxy resin. More preferably, at least one selected from the group consisting of bisphenol A type epoxy resin and naphthalene type epoxy resin.

When an epoxy resin is used, an epoxy hardener can also be used. Examples of the epoxy curing agent include an amine curing agent, an oxime curing agent, an imidazole curing agent, a phenol curing agent, an acid anhydride curing agent, or the like, or an epoxy addition product or a microencapsulation. From the viewpoint of viscosity stability when the thermosetting resin composition is used as a varnish, it is preferred to be an amine hardener and a microphone. An azole hardener. The epoxy curing agent may be used alone or in combination of two or more.

The bimaleimide resin is exemplified by, for example, "BMI-S" (manufactured by Mitsui Chemicals Co., Ltd.) of 4,4'-phenylmethane bismaleimide, and polyphenylmethane bismaleimide. "BMI-M-20" (Mitsui Chemical Co., Ltd.). The bismaleimide resin may be used alone or in combination of two or more.

The isocyanate resin is not particularly limited, and examples thereof include a novolak type (phenol novolak type, alkylphenol novolak type, etc.) isocyanate resin, a dicyclopentadiene type cyanate resin, and a bisphenol type (bisphenol A type). , a bisphenol F type, a bisphenol S type, etc.) a cyanate resin, and a part of the triazine-formed prepolymer. Specific examples of the cyanate resin are bisphenol A diisocyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene)), 4,4'-Asia. Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-dual ( 4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3- Difunctional of bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether a cyanate resin, a polyfunctional cyanate resin derived from a phenol novolac, a cresol novolak, a phenol resin containing a dicyclopentadiene structure, a part of the cyanate resin, a triazine-based polymer, etc. . These may be used alone or in combination of two or more. The commercially available cyanate resin is exemplified by, for example, a phenol resin having a dicyclopentadiene structure (manufactured by JAPAN LONZA Co., Ltd., DT-4000, DT-7000) and a bisphenol type cyanate resin "Primaset BA200". (LONZA (share) system), "Primaset BA230S" "Primaset LECY" (manufactured by RONZA Co., Ltd.) and bisphenol H-type cyanate resin, "Arocy L10" (manufactured by VANTICO Co., Ltd.), and "novolak type cyanate resin" Primaset PT30" (manufactured by LONZA Co., Ltd.), "Arocy XU371" (manufactured by VANTICO Co., Ltd.), and "Arocy XP71787.02L" (manufactured by VANTICO Co., Ltd.) of dicyclopentadiene type cyanate resin. The cyanate resin may be used alone or in combination of two or more.

The bisallyl nadic ylidene imide resin is exemplified by "BANI-M" (manufactured by Maruzen Petrochemical Co., Ltd.) of, for example, diphenylmethane-4,4'-bisallyl nadic ylidene. The diallyl nadic ylidene imine resin may be used alone or in combination of two or more.

Examples of the vinyl benzyl ether resin are, for example, V-1000X (manufactured by Showa Polymer Co., Ltd.), U.S. Patent No. 4,116,936, U.S. Patent No. 4,170,711, U.S. Patent No. 4,278,708, and Japanese Patent Laid-Open No. Hei 9-31006 No. 2001-181383, JP-A-2001-253992, JP-A-2003-277440, JP-A-2003-283076, and International Publication No. 02/083610 . The vinyl benzyl ether resin may be used alone or in combination of two or more.

Examples of the benzoxazine resin include, for example, "B-a type benzoxazine" and "B-m type benzoxazine" manufactured by Shikoku Kasei Co., Ltd., and the like. The benzoxazine resin may be used alone or in combination of two or more.

The polymer of the bismaleimide compound and the diamine compound as a thermosetting resin is exemplified by, for example, PRINTEQ (shares). "TECHMITE E2020" and so on. The polymer of the bismaleimide compound and the diamine compound may be used alone or in combination of two or more.

The thermosetting resin as the component (B) is preferably an epoxy resin, more preferably a liquid epoxy resin. The term "liquid epoxy resin" as used herein means a liquid epoxy resin at 25 ° C. The liquid epoxy resin is preferably a liquid epoxy resin having an aromatic ring, more preferably a liquid bisphenol A type epoxy resin, a liquid bisphenol F type epoxy resin, and a liquid naphthalene type epoxy resin. At least one selected from the group selected is preferably at least one selected from the group consisting of liquid bisphenol A type epoxy resin and liquid naphthalene type epoxy resin.

The content of the thermosetting resin of the component (B) is preferably from 15 to 80% by weight based on 100 parts by weight of the polyimine resin of the component (A), from the viewpoint of the degree of curing of the resin composition and the flexibility of the cured product. The portion is preferably 30 to 80 parts by weight, more preferably 40 to 70 parts by weight.

The total amount of the component (A) and the component (B) is preferably in the nonvolatile value of the thermosetting resin composition in consideration of the chemical resistance of the cured product and the other components in the thermosetting resin composition. It is 5 to 50% by weight, more preferably 10 to 30% by weight. Here, the non-volatile content of the thermosetting resin composition means a total of the remaining components of the volatile solvent removed from the thermosetting resin composition.

<Inorganic filler>

The thermosetting resin composition of the present invention may further contain one or more inorganic fillers. By using an inorganic filler, the coefficient of linear thermal expansion of the insulating layer obtained from the thermosetting resin composition can be lowered. As none The machine filler is exemplified by, for example, cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate. , barium titanate, calcium carbonate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among them, cerium oxide such as amorphous cerium oxide, pulverized cerium oxide, lanthanum oxidized cerium, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., is more preferably melt oxidized based on improvement of filling property.矽, spherical yttrium oxide, and more preferably spherical fused yttrium oxide. The commercially available spherical molten cerium oxide is exemplified by "SO-C2" and "SO-C1" manufactured by ADOMATEX Co., Ltd., and the like.

The average particle diameter of the inorganic filler is not particularly limited, but it is necessary to have a low-roughness in order to form fine wiring after roughening the surface of the insulating layer, and to have a good through-hole shape by laser processing. The viewpoint is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the thermosetting resin composition is used as a varnish, the average particle diameter is preferably 0.01 μm or more, more preferably 0.03 μm or more, and still more preferably 0.05 μm from the viewpoint of preventing the varnish from increasing in viscosity and reducing workability. The above is more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle diameter of the above inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be determined on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. The measurement sample can be preferably used in which an inorganic filler is dispersed in water by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, we can use the market (stock) LA-950 and so on.

In order to reduce the linear thermal expansion coefficient of the insulating layer (cured material) obtained from the thermosetting resin composition, the content of the inorganic filler is preferably 50% by weight or more in the nonvolatile content of the thermosetting resin composition. It is preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more. On the other hand, in terms of preventing the brittleness of the insulating layer or the surface of the insulating layer after the roughening treatment from being low in roughness, the non-volatile content of the thermosetting resin composition is preferably 95% by weight or less. More preferably, it is 93% by weight or less, more preferably 90% by weight or less, and particularly preferably 85% by weight or less.

As the inorganic filler, one or more inorganic fillers which are surface-treated with a surface treatment agent are preferably used. Examples of the surface treatment agent include an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a styrene decane coupling agent, an acrylate decane coupling agent, an isocyanate decane coupling agent, and a thioether decane. A coupling agent, a vinyl decane coupling agent, a decane coupling agent, an organic decane compound, a titanate coupling agent, and the like. The dispersibility or moisture resistance of the inorganic filler can be improved by surface treatment.

Specific surface treatment agents are exemplified by 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldiethoxymethyldecane, and N-phenyl-3. -Aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2- An amine decane coupling agent such as aminoethyl)-3-aminopropyldimethoxymethyl decane; 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyl(dimethoxy)methylnonane, glycidol Epoxy decane coupling agent such as butyl trimethoxy decane or 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane; 3-mercaptopropyltrimethoxy decane, 3-mercaptopropyl propyl a mercapto decane coupling agent such as triethoxy decane, 3-mercaptopropylmethyldimethoxydecane, 11-decylundecyltrimethoxydecane; benzene such as p-styryltrimethoxydecane Vinyl decane coupling agent; 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyldimethoxydecane An acrylate decane coupling agent such as 3-methacryloxypropyltriethoxydecane or 3-methylpropenyloxypropyldiethoxydecane; 3-isocyanatepropyltrimethoxy Isocyanate decane coupling agent such as decane; thioether decane such as bis(triethoxydecylpropyl)disulfide or bis(triethoxydecylpropyl)tetrasulfide Mixture; methyltrimethoxydecane, octadecyltrimethoxydecane, phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolyl decane, triazine decane, third butyl a decane coupling agent such as a trimethoxy decane; hexamethyldiazane, 1,3-divinyl-1,1,3,3-tetramethyldiazepine, hexaphenyldiazoxide Alkane, triazane, cyclotriazane, octamethylcyclotetraazane, hexabutyldioxane, hexaoctyldioxane, 1,3-diethyltetramethyldifluorene Azane, 1,3-di-n-octyltetramethyldiazepine, 1,3-diphenyltetramethyldiazide, 1,3-dimethyltetraphenyldioxane, 1 ,3-diethyltetramethyldiazepine, 1,1,3,3-tetraphenyl-1,3-dimethyldioxane, 1,3-dipropyltetramethyldifluorene Azane, hexamethylcyclotriazane, dimethylamino three An organic sulfonium compound such as methyl decazane or tetramethyldiazane; tetra-n-butyl titanate dimer, isopropyl oxyhydroxide octanediol, tetra-n-butyl titanate, octanediol acid Titanium, diisopropyl titanium oxide bis(triethanol aluminate), dihydroxy titanium dilactate, dihydroxy bis(ammonium lactate) titanium, bis(dioctyl pyrophosphate) ethylene titanate, double (two Octyl pyrophosphate)oxyacetate titanate, tri-n-butoxide titanium monostearate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropyl (dioctylphosphite) titanate, tetraoctylbis(di-tridecylphosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl) Bis(di-tridecyl)phosphite titanate, isopropyl trioctadecyl titanate, isopropyl tricumylphenyl titanate, isopropyl triisostearate titanate, Isopropylisostearyl methacrylate, isopropyl dimethyl propylene decyl isostearyl phthalate, isopropyl tris(dioctyl phosphite) titanate, isopropyl Tridecylbenzenesulfonate titanate, isopropyl ginseng (dioctyl pyrophosphate) titanate, isopropyl -Tris (N- acyl-aminoethyl. Aminoethyl) titanate, etc. The titanate coupling agents. Among these, an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, and an organic decazane compound are preferable. Commercially available products are "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-amino group) "propyl trimethoxy decane", "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

Surface treatment method of inorganic filler with surface treatment agent It is not particularly limited and is exemplified by a dry method or a wet method. As a dry method, the inorganic filler is fed into, for example, a rotary kneading machine, and an alcohol solution or an aqueous solution of the surface treatment agent is added dropwise or sprayed with stirring, stirred, and classified by a sieve, followed by heating. A method of dehydrating and condensing a surface treatment agent with an inorganic filler. As a wet method, for example, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, it is filtered, dried, and classified by a sieve, and then, the surface treatment agent and the inorganic filler are dehydrated by heating. The method of condensation. Further, a surface treatment agent may be added to the surface treatment of the integrally-blended inorganic filler in the thermosetting resin composition.

<hardening accelerator>

The thermosetting resin composition of the present invention may further contain one or more hardening accelerators. The thermosetting resin of the component (B) can be effectively cured by the curing accelerator. The hardening accelerator is not particularly limited, and examples thereof include an imidazole-based hardening accelerator, an amine-based hardening accelerator, an anthraquinone-based hardening accelerator, and an oxime-based hardening accelerator.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitic acid Salt, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2 '-Ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]-Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4- Methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzimidazole An imidazole compound such as chloride, 2-methylimidazoline or 2-phenylimidazoline, and an adduct of an imidazole compound and an epoxy resin. The imidazole hardening accelerator may be used alone or in combination of two or more.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-cis (dimethylaminomethyl). An amine compound such as phenol or 1,8-diazabicyclo(5,4,0)-undecene (DBU). The amine-based hardening accelerator may be used alone or in combination of two or more.

Examples of the lanthanide hardening accelerator are, for example, dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl fluorene, 1-phenyl fluorene, 1-(o-tolyl) fluorene, and Methyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl- 1,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1 , 1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like. Lanthanide hardening accelerator can only make One type may be used in combination of two or more types.

Examples of the lanthanide hardening accelerator include, for example, triphenylphosphine, lanthanum borate, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonate, (4-A). Phenylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. The lanthanum-based hardening accelerator may be used alone or in combination of two or more.

When the curing accelerator is used, the content thereof is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass, per 100 parts by mass of the thermosetting resin of the component (B).

<Other ingredients>

The thermosetting resin composition of the present invention may be blended with other components as needed within a range not inhibiting the effects of the present invention. Examples of other components include organic fillers such as strontium powder, nylon powder, fluorine powder, and rubber particles; tackifiers such as Oluben and Benton; polyfluorene-based, fluorine-based, and polymeric antifoaming agents or leveling agents; and thiazole. An adhesion imparting agent such as a decane coupling agent or a triazole decane coupling agent; phthalocyanine. Blue, turnip. Green, iodine. Coloring agents such as green, disazo yellow, carbon black; organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, antimony-based flame retardants, metal hydroxides, etc.; .

The thermosetting resin composition of the present invention can be mixed by appropriately mixing the above components, and if necessary, by a mixing means such as a three-roller, a ball mill, a bead mill, a sand mill, or a super-kneading machine or a planetary kneader. Modulation by mixing or mixing. Further, a solvent may be further added It is prepared as a resin paint.

The solvent which can be used for the thermosetting resin composition (resin varnish) is exemplified by a ketone such as acetone, methyl ethyl ketone or cyclohexanone; ethyl acetate, butyl acetate, fibrin acetate, and propylene glycol. Esters such as methyl ether acetate and diethylene glycol monoethyl ether acetate; ethers such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamidine A guanamine-based solvent such as an amine, dimethylacetamide or N-methylpyrrolidone. The solvent may be used alone or in combination of two or more. Among these, ketones and esters are preferred, and diethylene glycol monoethyl ether acetate and methyl ethyl ketone are preferred.

When the solvent is used, the content thereof is preferably from 10 to 50% by weight, more preferably from 20 to 40% by weight, based on the viscosity of the thermosetting resin composition (resin varnish).

The cured product formed of the thermosetting resin composition of the present invention can be preferably used as an insulating layer of a circuit board. The insulating layer can be formed by applying a thermosetting resin composition in the form of a resin varnish to a substrate, or can be formed on a support film having a film formed of a layer formed of a thermosetting resin composition.

(following the film)

The present invention provides an adhesive film having a layer formed from the above thermosetting resin composition on a support. The film of the present invention can be applied to a support by a method known to those skilled in the art, for example, a resin paint obtained by dissolving a thermosetting resin composition in a solvent, and then coated on a support by a die coater or the like. Or removing the solvent by hot air blowing, etc., and forming on the support It is produced by the method of the thermosetting resin composition layer.

The solvent is usually removed so that the solvent content (residual solvent amount) in the thermosetting resin composition layer is 10% by weight or less, preferably 6% by weight or less. The solvent removal (drying) conditions vary depending on the amount of the solvent in the resin varnish and the boiling point of the solvent. For example, when a resin paint containing 30 to 60% by weight of a solvent is used, it is usually dried at 50 to 150 ° C for about 3 to 10 minutes.

The thickness (thickness after drying) of the thermosetting resin composition layer formed in the film is preferably more than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm. Therefore, the thickness of the thermosetting resin composition layer is preferably 10 to 200 μm, and more preferably 15 to 100 μm from the viewpoint of film formation. More preferably 20~60μm.

Examples of the support include a film of a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, and a polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") or polyethylene naphthalate. Film, polycarbonate film, polyimide film and other plastic film. It is also possible to use a release paper, a metal foil such as a copper foil or an aluminum foil. Among these, from the viewpoint of general availability, a plastic film is preferred, and a PET film is more preferred. The support and the protective film described later may be subjected to surface treatment such as matting treatment or corona treatment, or may be demolded by a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent. The agent is subjected to a release treatment. The thickness of the support is not particularly limited, and is preferably from 10 to 150 μm, more preferably from 25 to 50 μm.

The surface of the thermosetting resin composition layer which is not adhered to the support may be further laminated with a protective film according to the support. Protect the thickness of the film and It is not particularly limited, but may be, for example, 1 to 40 μm, preferably 5 to 20 μm. By laminating the protective film, it is possible to prevent dust or scratches from adhering to the surface of the thermosetting resin composition layer. The film can then be wound into a roll for storage.

<Printed wiring board>

The present invention provides a printed wiring board having a cured product formed of the above-described thermosetting resin composition as an insulating layer. The printed wiring board of the present invention is exemplified by a hard circuit board, a flexible circuit board, a single-sided laminated board, a thin substrate, and the like. Among these, a flexible circuit board is preferred. An example of a method of manufacturing a printed wiring board using the adhesive film manufactured as described above will be described.

First, the adhesive film is laminated on one or both sides of the inner layer circuit substrate using a vacuum laminator. Examples of the substrate used for the inner layer circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the term "inner layer circuit substrate" means a conductor layer (circuit) formed by patterning on one surface or both surfaces of the substrate. Further, in the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, the one or both sides of the outermost layer of the multilayer printed wiring board are also patterned by the patterned conductor layer (circuit). It is called the inner layer circuit board. Further, the surface of the conductor layer may be subjected to a roughening treatment such as blackening treatment or copper etching.

In the above lamination, when the film has a protective film, after the protective film is removed, the film and the circuit substrate are preheated as needed, and the circuit substrate is laminated while being pressed and heated. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by vacuum lamination is preferably used. The lamination conditions are not particularly limited, and it is preferred that the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably set to 1 to 11 kgf/cm ² (9.8 × 10). ⁴ to 107.9 × 10 ⁴ N/m ² ), the pressing time (lamination time) is preferably 5 to 180 seconds, and the pressure is laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. Moreover, the lamination method may be a batch type or a continuous type using a reel. Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machines include, for example, a vacuum coating machine manufactured by Nichigo Morton Co., Ltd., a vacuum pressure laminating machine manufactured by a famous machine manufacturer, and a drum type dry coating manufactured by Hitachi Industrial Co., Ltd. Cloth machine, vacuum laminator made by Hitachi AIC (share).

After laminating the film on the inner layer circuit board, the film is cooled to room temperature, and then peeled off when the support is peeled off, and the thermosetting resin composition is thermally cured to form a cured product, thereby being able to be formed on the inner circuit board. An insulating layer is formed. The thermosetting condition may be appropriately selected depending on the type and content of the resin component in the thermosetting resin composition, but it is preferably from 150 to 220 ° C for 20 to 180 minutes, more preferably from 160 to 210 ° C for 30 to 120. Choose within the range of minutes. After the insulating layer (cured material) is formed, the support may be peeled off after hardening, as long as the support is not peeled off before hardening. The thickness of the insulating layer is preferably from 10 to 200 μm as the thickness of the thermosetting resin composition layer formed in the film, and is preferably from 15 to 100 μm, more preferably from 20 to 60 μm, from the viewpoint of film formation.

Next, the insulating layer formed on the inner circuit substrate is subjected to drilling to form a through hole and a through hole. Hole drilling can be done by, for example, a drilling machine, Conventional methods such as laser and plasma, and can be combined as needed, but the most common method is laser drilling with a carbon dioxide gas laser, a YAG laser, or the like. In the case where the support is not peeled off before the hole processing, it may be peeled off here.

Next, the surface of the insulating layer is roughened. The dry roughening treatment is exemplified by plasma treatment or the like, and the wet roughening treatment is exemplified by a swelling treatment of the swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid. The wet roughening processor is preferred in that the anchoring in the perforation is removed based on the anchoring which can form irregularities on the surface of the insulating layer. The swelling treatment of the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably immersing for 8 to 15 minutes at 55 to 70 ° C). The swelling liquid is exemplified by an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, which is exemplified by, for example, a sodium hydroxide solution, a potassium hydroxide solution or the like. Commercially available swellable liquids include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by ATOTECH Co., Ltd., Japan. The oxidizing agent is subjected to a roughening treatment at 60 to 80 ° C to immerse the insulating layer in the oxidizing agent solution for 10 to 30 minutes (preferably, immersion at 70 to 80 ° C for 15 to 25 minutes). The oxidizing agent may, for example, be an alkaline permanganic acid solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Further, the permanganate concentration in the alkaline permanganic acid solution is preferably set to 5 to 10% by weight. The commercially available oxidizing agent is exemplified by an alkaline permanganic acid solution such as Concentrate Compact CP or Doesing Solution Securiganth P manufactured by Atotech Co., Ltd., Japan. Among the neutralizing liquids The treatment is carried out by immersing in a neutralization solution at 30 to 50 ° C for 3 to 10 minutes (preferably at 35 to 45 ° C for 3 to 8 minutes). The neutralizing liquid is preferably an acidic aqueous solution, and the commercial product is listed as Reduction Solution Securiganth P manufactured by ATOTECH Co., Ltd., Japan.

The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably from 220 to 1,000 nm, more preferably from 300 to 800 nm, in terms of the formation of the fine wiring and the stability of the peak intensity. Specifically, a non-contact type surface roughness meter (WYKO NT3300 manufactured by VEECO Instruments Co., Ltd.) was used, and the Ra value was obtained by using a VSI contact mode and a 50-fold lens to obtain a measurement range of 121 μm × 92 μm.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. Dry plating can be carried out by a conventional method such as vapor deposition, sputtering, or ion plating. The wet plating is a method in which a conductor layer is formed by combining electroless plating and electrolytic plating, a plating resist having a pattern opposite to that of the conductor layer is formed, and a conductor layer is formed only by electroless plating.

The peeling strength between the conductor layer and the insulating layer is preferably 0.5 kgf/cm or more, more preferably 0.6 kgf/cm or more, and still more preferably 0.7 kgf/cm or more. The upper limit of the peeling strength is not particularly limited and is, for example, 1.5 kgf/cm or less, preferably 1.0 kgf/cm or less.

Subsequent methods of forming the pattern may be carried out by repeating the above-described series of steps, for example, by a subtractive method, a semi-additive method, or the like as known to those skilled in the art, and multi-layer lamination is performed to form a multilayer printed wiring board.

<Wafer Level Wafer Size Package>

The present invention provides a wafer level wafer size package having a cured product formed of the above-described thermosetting resin composition as an insulating layer. The thermosetting resin composition may be laminated on both sides of a wafer level wafer size package, or may be laminated on one side. Wafer-level wafer size packaging can explore a variety of configurations, but is broadly divided into a fan in configuration and a fan out configuration. The thickness of the germanium wafer is preferably from 50 to 150 μm, more preferably from 80 to 120 μm, from the viewpoint of film formation.

As an example of a method of manufacturing a wafer level wafer size package having a fan-in structure using the adhesive film manufactured as described above, a method including the following steps is exemplified.

(1) A step of forming a circuit or an electrode pad on a germanium wafer.

(2) A step of laminating the adhesive film of the present invention on a wafer.

(3) A step of hardening the film, peeling off the support, performing opening, and performing desmear, and forming a rewiring layer by electroless plating and electrolytic plating.

(4) Repeat steps (2) and (3) from the rewiring layer as needed.

(5) A step of forming a solder ball on the rewiring layer.

(6) The step of performing dicing.

An example of a method of manufacturing a wafer level wafer size package which is another fan-in structure is a method described in Japanese Patent No. 3618330. Moreover, as an example, the following steps are included as an example.

(1) A step of forming a circuit element having a specific function and a plurality of electrode pads electrically connected to the circuit element to form a germanium wafer.

(2) A step of forming a columnar electrode on the electrode pad portion on the wafer.

(3) A step of bonding the bonding film of the present invention to the surface of the columnar electrode surface and hardening, and peeling off the support to form an insulating layer.

(4) A step of appropriately polishing the insulating layer and the upper surface of the columnar electrode to expose the upper surface of the columnar electrode.

(5) A step of forming a solder ball on the exposed columnar electrode.

(6) The step of performing dicing.

As an example of a method of manufacturing a wafer level wafer size package having a fan-out structure using the adhesive film produced as described above, a method including the following steps is exemplified.

(1) A step of dicing a germanium wafer to form a wafer monolith.

(2) A step of fixing the wafer monolithic barrier film to the support substrate.

(3) A step of laminating the adhesive film of the present invention from a single side of the wafer.

(4) A step of hardening the film, peeling off the support, performing opening, performing desmear, and forming a rewiring layer by electroless plating and electrolytic plating.

(5) The step of laminating the film as needed.

(6) A step of forming a solder ball on the rewiring layer.

An example of a method of manufacturing a wafer level wafer size package of another fan-out structure is a method described in JP-A-2005-167191. Moreover, as an example, the following steps are included as an example.

(1) A step of forming a circuit element having a specific function and a plurality of electrode pads electrically connected to the circuit element to form a germanium wafer.

(2) A step of dicing a single piece of a semiconductor wafer.

(3) The step of arranging and fixing the thin film on the support by disposing the semiconductor wafer so that the distance between the semiconductor wafers has a sufficient space for forming a fan-out ball array in a subsequent step.

(4) A step of laminating the adhesive film of the present invention in such a manner that the surface of the semiconductor wafer is filled from the surface of the semiconductor wafer.

(5) A step of hardening the film, peeling off the support, etching the insulating layer on the pad of the semiconductor wafer, forming an opening, and forming a conductive layer in the opening.

(6) A step of forming a fan-out pattern and an electrode on the insulating layer using a photoresist to form a solder ball on the electrode pad.

[Examples]

In the following, the present invention will be specifically described by using the synthesis examples, the examples, and the comparative examples. However, the present invention is not limited to the following synthesis examples and the like, and may be appropriately modified and implemented in a range suitable for the above-mentioned/the following description. These are all included in the technical scope of the present invention. In addition, "%" and "parts" described below mean "% by weight" and "parts by weight" unless otherwise specified.

The equivalent amount described in the following synthesis examples and the like means the molecular weight of the compound having the functional group of the equivalent object divided by the value of the functional group of the compound, that is, the molecular weight per one functional group. For example, the acid anhydride equivalent means a molecular weight of a compound having an acid anhydride (carbonyloxycarbonyl group) divided by a value of the number of acid anhydride groups of the compound contained in one molecule, that is, per 1 acid. The molecular weight of the anhydride group.

Synthesis Example 1: Production of Polyimine Resin (A1)

In the reaction vessel, polycarbonate diol (number average molecular weight: about 2,000, hydroxyl equivalent: 1,000, nonvolatile matter: 100%, "C-2015N" manufactured by KURARAY Co., Ltd.) 80 g and dibutyltin dilaurate 0.01 g were used. The solution was uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate ("Ethylene diethylene glycol acetate" manufactured by DAICEL Co., Ltd.). Next, the mixture was heated to 50 ° C, and further, 13.9 g of toluene-2,4-diisocyanate (isocyanate equivalent: 87.08) was added while stirring, and the reaction was carried out for about 3 hours. Next, after cooling the reaction to room temperature, 14.3 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent: 161.1), 0.11 g of triethylenediamine, and diethylene glycol monoethyl ether B were added thereto. 70.5 g of an acid ester ("Ethyl diglycol acetate" manufactured by DAICEL Co., Ltd.) was heated to 130 ° C with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^{-1 was} carried out by FT-IR. It was confirmed that the NCO peak disappeared as the end point of the reaction, and after the reaction product was cooled to room temperature, it was filtered through a filter cloth having a mesh size of 100 μm to obtain a polyazide having a quinone imine structure and a urethane and carbonate structure. Amine resin (A1) varnish.

The viscosity and nonvolatile content of the obtained polyimine resin (A1) varnish and the number average molecular weight and glass transition temperature of the polyimine resin (A1) are described below.

Polyimide resin (A1) varnish viscosity: 6Pa. s (25 ° C, E-type viscometer)

Non-volatile content of polyimine resin (A1) varnish: 50%

The average molecular weight of the polyimine resin (A1): 11,500

Glass transition temperature of polyimine resin (A1): -1 ° C

Synthesis Example 2: Production of Polyimine Resin (A2)

In the reaction vessel, polycarbonate diol (number average molecular weight: about 1,000, hydroxyl equivalent: 500, nonvolatile content: 100%, "C-1015N" manufactured by Kuraray Co., Ltd.), 80 g of dibutyltin dilaurate and 0.01 g of dibutyltin dilaurate were added. The solution was uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate ("Ethylene diethylene glycol acetate" manufactured by DAICEL Co., Ltd.). Next, the mixture was heated to 50 ° C, and 27.8 g of toluene-2,4-diisocyanate (isocyanate equivalent: 87.08) was further added thereto with stirring, and the reaction was carried out for about 3 hours. Next, after cooling the reaction to room temperature, 14.3 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent: 161.1), 0.12 g of triethylenediamine and diethylene glycol monoethyl ether B were added thereto. 84.0 g of an acid ester ("Ethyl diglycol acetate" manufactured by DAICEL Co., Ltd.) was heated to 130 ° C with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ^{-1 was} carried out by FT-IR. It was confirmed that the NCO peak disappeared as the end point of the reaction, and after the reaction product was cooled to room temperature, it was filtered through a filter cloth having a mesh size of 100 μm to obtain a polyazide having a quinone imine structure and a urethane and carbonate structure. Amine resin (A2) varnish.

The viscosity and nonvolatile content of the obtained polyimine resin (A2) varnish and the number average molecular weight and glass transition temperature of the polyimine resin (A2) are described below.

Polyimide resin (A2) varnish viscosity: 3Pa. s (25 ° C, E-type viscometer)

Non-volatile content of polyimine resin (A2) varnish: 50%

Number average molecular weight of polyimine resin (A2): 8,500

Glass transition temperature of polyimide resin (A2): 5 ° C

Example 1

40 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "jer828EL" manufactured by Mitsubishi Chemical Co., Ltd.), and a hardening accelerator (imidazole derivative, "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.) 1 PCT, 260 parts of polyimine resin (A1) varnish, 300 parts of methyl ethyl ketone (hereinafter referred to as "MEK"), liquid naphthalene type epoxy resin (epoxy equivalent: 151, DIC (share) system" HP-4032") 20 parts and inorganic fillers {Spherical molten cerium oxide surface treated with phenylamino decane coupling agent (KBM573) manufactured by Shin-Etsu Chemical Co., Ltd.) (SO-made by ADOMATEX Co., Ltd.) C2", average particle diameter: 0.5 μm)} 920 parts of the mixture, uniformly dispersed by a high-speed rotary kneading machine to prepare a resin varnish. The composition of the obtained resin varnish (except solvent) is shown in Table 1 below.

Example 2

40 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "jer828EL" manufactured by Mitsubishi Chemical Co., Ltd.), and a hardening accelerator (imidazole derivative, "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.) 1 Parts, 260 parts of polyimine resin (A2) varnish, 300 parts of MEK, 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent: 151, "HP-4032" made by DIC) and inorganic fillers { A spherical molten cerium oxide ("SO-C2" manufactured by ADOMATEX Co., Ltd.) which is surface-treated with a phenylamino decane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). Average particle diameter: 0.5 μm)} 920 parts of the mixture, uniformly dispersed by a high-speed rotary kneading machine to prepare a resin varnish. The composition of the obtained resin varnish (except solvent) is shown in Table 1 below.

Comparative example 1

40 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "jer828EL" manufactured by Mitsubishi Chemical Co., Ltd.), and a hardening accelerator (imidazole derivative, "2P4MZ" manufactured by Shikoku Kasei Co., Ltd.) 1 8.6 parts of acrylate copolymer ("SG-P3" made by NAGASE CHEMICALS), 300 parts of MEK, and 20 parts of liquid naphthalene type epoxy resin (epoxy equivalent: 151, "HP-4032" made by DIC) Inorganic filler material {Spherical molten cerium oxide ("SO-C2" manufactured by ADOMATEX Co., Ltd.), which is surface-treated with a phenylamino decane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter: 0.5 μm)} 920 parts of the mixture were uniformly dispersed by a high-speed rotary kneading machine to prepare a resin varnish. The composition of the obtained resin varnish (except solvent) is shown in Table 1 below.

Comparative example 2

40 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent: 180, "jer828EL" manufactured by Mitsubishi Chemical Corporation), and a naphthalene type tetrafunctional epoxy resin (epoxy equivalent: 163, manufactured by DIC) 22 parts of HP-4710"), 1 part of hardening accelerator (imidazole derivative, "2P4MZ" made by Shikoku Chemical Co., Ltd.), phenoxy resin solution ("YX-6954" manufactured by Mitsubishi Chemical Corporation) and MEK and Mixture solution of cyclohexanone, non-volatile: 30%) 20 parts, MEK solution of naphthol-based hardener (hydroxy equivalent: 215, "SN-485" manufactured by Nippon Steel & Sumitomo Co., Ltd.) (non-volatile: 50%) 30 parts, MEK 30 parts and inorganic fillers {Phosphorically fused cerium oxide surface treated with phenylamino decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (ADOMATEX ( "SO-C2", average particle size: 0.5 μm)} 300 parts of the mixture, uniformly dispersed by a high-speed rotary kneading machine to prepare a resin varnish. The composition of the obtained resin varnish (except solvent) is shown in Table 1 below.

<Evaluation of hydrophilicity>

Each of the resin varnishes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was applied to a support (polyethylene terephthalate film) so that the thickness of the thermosetting resin composition layer after drying was 80 μm. The film was applied by a die coater and dried at 80 to 120 ° C (average 100 ° C) for 10 minutes to form a thermosetting resin composition layer on the support to produce a film. Using a batch vacuum pressure laminator ("CVP-600" manufactured by NICHIGO MORTON Co., Ltd.), the adhesive film was bonded to a 6-inch wafer (625 μm), and the support was peeled off to form a thermosetting resin. The layer was heated at 160 ° C for 60 minutes to form a hardened layer. The water contact angle of the obtained cured layer was measured by a contact angle meter ("DM-500" manufactured by Kyowa Interface Science Co., Ltd.).

When the water contact angle is less than 60 degrees, it is evaluated as "good ○", 60 to 80 degrees is evaluated as "slightly bad △", and when it exceeds 80 degrees, it is evaluated as "bad ×". The results are shown in Table 1 below.

<Evaluation of elastic modulus>

On the support (polyethylene terephthalate film), Example 1 And each of the resin varnishes obtained in Comparative Examples 1 and 2 was applied by a die coater so as to have a thickness of the thermosetting resin composition layer after drying of 80 μm at 80 to 120 ° C (average 100 ° C). After drying for 10 minutes, a thermosetting resin composition layer was formed on the support to produce a film. The film was thermally cured at 180 ° C for 2 hours, and a cured layer was formed from the thermosetting resin composition layer. The support was peeled off from the cured layer, and a tensile test was performed in accordance with JIS K7127 using a TENSILON universal testing machine (manufactured by A&D Co., Ltd.), and the elastic modulus of the cured layer was measured.

Those having an elastic modulus of 10 GPa or less were evaluated as "good ○", and those having an elastic modulus exceeding 10 GPa were evaluated as "bad x". The results are shown in Table 1 below.

As shown by the water contact angle shown in Table 1, the cured layer obtained by using the resin varnish of Examples 1 and 2 which satisfies the requirements of the present invention, the polyimine resin (A1) or (A2), is compared with The cured product layer obtained from the resin varnishes of Comparative Examples 1 and 2 which were not used in the above polyimine resin was excellent in hydrophilicity. Further, the cured product obtained from the resin varnish of Comparative Example 2 in which the phenoxy resin or the naphthol-based curing agent was used without using the above-mentioned polyimide resin had a high modulus of elasticity although the content of the inorganic filler was small.

[Industrial availability]

The thermosetting resin composition of the present invention is useful for forming an insulating layer of a circuit board such as a flexible circuit board or a wafer level wafer size package.

The present application is based on Japanese Patent Application No. 2015-023364, the entire disclosure of which is incorporated herein.

Claims (20)

A thermosetting resin composition comprising (A) a polyimine resin having a structure represented by formula (1-a) and a structure represented by formula (1-b), Wherein R1 represents a residue after removing a hydroxyl group of a polycarbonate diol, R2 represents a residue after removing a carboxyl group or an acid anhydride group of a polybasic acid or an acid anhydride thereof, and R3 represents a residue after removing an isocyanate group of a diisocyanate compound; ], and (B) from epoxy resin, bismaleimide resin, cyanate resin, bisallylnadic imide resin, vinyl benzyl ether resin, benzoxazine One or more kinds of thermosetting resins selected from the group consisting of a resin and a polymer of bismaleimide and diamine. The thermosetting resin composition of claim 1, wherein the polyimine resin of the component (A) has a configuration represented by the formula (abc): [wherein, R1 to R3 are as described in the claim 1, and n and m represent integers]. The thermosetting resin composition of claim 1 or 2, wherein the polycarbonate diol has a number average molecular weight of 500 to 5,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein R1 is a divalent group represented by formula (1-c): [wherein, k+1 R4 each independently represent an alkylene group having 1 to 20 carbon atoms which may have a substituent, and k represents an integer of 5 to 30]. The thermosetting resin composition according to any one of the above claims 1 to 4, wherein R2 represents one or more selected from the group consisting of a tetravalent group represented by any one of the following formulas: Wherein A represents an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(CCl ₃ ) ₂ , In the above, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms]. The thermosetting resin composition according to any one of claims 1 to 5, wherein R3 represents one or more selected from the group consisting of two valent groups represented by any one of the following formulas: [In the formula, a hydrogen atom bonded to a carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms]. The thermosetting resin composition according to any one of claims 1 to 6, wherein the polyamidene resin of the component (A) has a number average molecular weight of 5,000 to 25,000. The thermosetting resin composition according to any one of claims 1 to 6, wherein the polyamidene resin of the component (A) has a number average molecular weight of 5,000 to 20,000. The thermosetting resin composition according to any one of claims 1 to 8, wherein the glass transition temperature of the polyimine resin of the component (A) is 30 ° C or lower. The thermosetting resin composition according to any one of claims 1 to 9, wherein the thermosetting resin of the component (B) is an epoxy resin. The thermosetting resin composition of claim 10, wherein the epoxy The resin has an epoxy equivalent of 90 to 500. The thermosetting resin composition of claim 10 or 11, wherein the epoxy resin is a liquid epoxy resin. The thermosetting resin composition according to any one of claims 1 to 12, wherein the content of the thermosetting resin of the component (B) is 15% by weight based on 100 parts by weight of the polyimine resin of the component (A). 80 parts by weight. The thermosetting resin composition according to any one of claims 1 to 13, which further comprises an inorganic filler. The thermosetting resin composition of claim 14, wherein the inorganic filler is cerium oxide. The thermosetting resin composition according to claim 14 or 15, wherein the content of the inorganic filler is 50 to 95% by weight based on the nonvolatile content of the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 16, which further contains a curing accelerator. An adhesive film having a layer formed of the thermosetting resin composition according to any one of claims 1 to 17 on a support. A printed wiring board having a cured product formed of the thermosetting resin composition according to any one of claims 1 to 17 as an insulating layer. A wafer-level wafer-size package having a cured product formed of the thermosetting resin composition according to any one of claims 1 to 17 as an insulating layer.