JP4815767B2 - Thermosetting resin composition and resin varnish using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which can sufficiently reduce transmission loss especially in high frequency bands and can form printed wiring boards in which adhesive forces between insulation layers and conductor layers are sufficiently strengthened, and to provide a resin varnish using the same. <P>SOLUTION: This thermosetting resin composition is characterized by comprising (A) component: a polyamideimide, and (B) component: a compound which has a functional group capable of reacting with the amide group of the polyamideimide and an ethylenic unsaturated bond. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a thermosetting resin composition and a resin varnish using the same.

  Mobile communication devices such as mobile phones, base station equipment, network-related electronic devices such as servers and routers, and large computers are required to transmit and process large amounts of information with low loss and high speed. Yes. In order to meet such demands, the frequency of electrical signals handled on a printed wiring board mounted on the above-described apparatus is increasing. However, the higher the frequency is, the easier the electric signal is attenuated, so the printed wiring board used in these fields needs to further reduce the transmission loss.

  In order to obtain a printed wiring board with low transmission loss, conventionally, a thermosetting resin material containing a fluorine-based resin having a low relative dielectric constant and dielectric loss tangent has been used as a substrate material for the printed wiring board. However, since a fluorine-based resin generally has a high melt viscosity and a relatively low fluidity, it is necessary to set high-temperature and high-pressure conditions during press molding. Moreover, as a printed wiring board material used for the above communication equipment, network-related electronic equipment, large computers, etc., processability, dimensional stability, and adhesion to metal plating are insufficient.

  Therefore, resin compositions containing triallyl cyanurate and triallyl isocyanurate shown in Patent Documents 1 to 3, which are thermosetting resins having a low relative dielectric constant and dielectric loss tangent, Patent Documents 1, 2, 4 And a resin composition containing polybutadiene as shown in 5, and a thermosetting polyphenylene ether provided with a radical crosslinkable functional group such as an allyl group as shown in Patent Document 6 and the above-mentioned triallyl cyanurate or triaryl. There has been proposed a method in which a resin composition containing allyl isocyanurate is used as a raw material for a dielectric material such as the electronic device. According to these patent documents, generally, the cured resin does not have many polar groups, so that it is possible to reduce transmission loss.

  However, in recent years, a resin having a low dielectric constant and a low dielectric loss tangent as described in Patent Documents 1 to 6 is used as a dielectric material, and only a reduction in electric signal transmission loss in an insulating layer (dielectric layer) has been achieved in recent years. This is inadequate as a measure for further increasing the frequency of electrical signals. In other words, electrical signal transmission loss is classified into loss due to the insulating layer (dielectric loss) and loss due to the conductor layer (conductor loss). Recently, not only reduction of dielectric loss but also conductor loss. The need for reducing the power consumption is not negligible. In particular, in most printed wiring boards (multilayer wiring boards) that have been put to practical use in recent years, the thickness of the insulating layer disposed between the signal layer and the ground layer, which are conductor layers, is relatively thin, 200 μm or less. When a resin exhibiting a certain low dielectric constant and dielectric loss tangent is used as the material of the insulating layer, the conductor loss rather than the dielectric loss is dominant as the transmission loss of the entire wiring board.

Further, Patent Documents 7 and 8 intend to provide a laminated board having excellent high-frequency characteristics, good heat resistance, peel strength, and electrical characteristics, and having a smooth manufacturing process, and a manufacturing method thereof. Then, a means for obtaining a copper-clad laminate by laminating a thermosetting prepreg such as a vinyl curable polybutadiene resin and a copper foil to which polybutadiene modified with epoxy, maleic acid, carboxylic acid or the like is attached is proposed. ing.
Japanese Examined Patent Publication No. 6-69746 Japanese Patent Publication No. 7-47689 JP 2002-265777 A Japanese Patent Publication No.58-21925 JP-A-10-117052 Japanese Patent Publication No. 6-92533 JP 54-74883 A JP 55-86744 A

  As a method for reducing the conductor loss, a metal foil having a small surface irregularity on the roughened surface (hereinafter referred to as “M surface”) side which is an adhesive surface between the conductor layer and the insulating layer, specifically, M There is a method of using a metal-clad laminate using a metal foil (hereinafter referred to as “low profile foil”) having a surface roughness (ten-point average roughness; Rz) of 4 μm or less.

  Therefore, the present inventors, including those described in Patent Documents 1 to 6, low dielectric constant, low dielectric loss tangent resin cured by polymerization of vinyl group and allyl group and the above-mentioned low profile foil The printed wiring board used together was examined in detail. As a result, the printed wiring board has a low polarity of the insulating layer, and the anchor effect due to the unevenness of the M surface of the metal foil is reduced, so that the adhesive force (bonding force) between the insulating layer and the conductor layer becomes weak. It has been found that easy delamination occurs between these layers. Such peeling becomes prominent when the printed wiring board is heated (particularly when heated after moisture absorption). Therefore, the present inventors have clarified that when the above-described resin is used as a dielectric material, there is a limit to achieving a sufficiently low transmission loss by employing a low profile foil.

  In addition, by applying the means described in Patent Documents 7 and 8, a printed wiring board is produced using a low profile copper foil having an M-plane Rz of 4 μm or less, thereby obtaining a sufficiently high copper foil peel strength. The present inventors have found that heat resistance (particularly heat resistance during moisture absorption) is reduced.

  Therefore, the present invention has been made in view of the above circumstances, and can form a printed wiring board that can sufficiently reduce transmission loss particularly in a high-frequency band and that has a sufficiently strong adhesive force between an insulating layer and a conductor layer. It is an object of the present invention to provide a possible thermosetting resin composition and a resin varnish using the same.

  The present inventors have developed a low-roughness metal foil, such as a low-profile foil, for thermosetting resins having a low dielectric constant, such as polybutadiene, triallyl isocyanurate and functionalized polyphenylene ether, as dielectric materials for the insulating layer. As a result of intensive studies to solve the above problems even when used in combination, the present invention has been completed.

  That is, the thermosetting resin composition of the present invention comprises (A) component; polyamideimide, (B) component; a functional group capable of reacting with the amide group of the polyamideimide, and having an ethylenically unsaturated bond. And a compound having the same.

  The thermosetting resin composition of the present invention comprises (A) component; polyamideimide, (C) component; a compound having two or more functional groups capable of reacting with the amide group of the polyamideimide, and (D) Component: (C) It has the functional group which can react with component, and contains the compound which has an ethylenically unsaturated bond, It is characterized by the above-mentioned.

  When the conductor layer and the insulating layer are connected using the thermosetting resin composition according to the present invention, an adhesive layer made of the thermosetting resin composition of the present invention is interposed between the conductor layer and the insulating layer. A printed wiring board is obtained. According to this adhesive layer, even when a metal foil having a small surface roughness such as a low profile foil and the above-mentioned dielectric material are used in combination as the conductor layer, a sufficiently high metal foil peeling strength can be secured. Therefore, when the thermosetting resin composition of the present invention is used, it is possible to sufficiently reduce the transmission loss in the high frequency band, and to form a printed wiring board with sufficiently strong adhesion between the insulating layer and the conductor layer. Can do.

In addition, high-frequency circuits used in electronic devices such as those described above require good impedance control as well as low transmission loss. To achieve this, the conductor pattern width in the signal layer is formed. Improvement of accuracy when doing so is an important point. When a metal foil having a small surface roughness such as a low profile foil can be used, the etching accuracy can be improved, which is effective for improving the accuracy in forming the conductor pattern width and for further fine patterning of the circuit. When the thermosetting resin composition of the present invention is used, a low profile foil is used as the metal foil, and even if a resin having a low dielectric constant and a low dielectric loss tangent is used for the insulating resin layer, it is sufficient between the insulating layer and the metal foil. Therefore, good impedance control can be realized.
From the above, the thermosetting resin composition of the present invention is suitably used for connecting the conductor layer and the insulating layer of the printed wiring board.

  The layer obtained by curing the adhesive layer according to the present invention (hereinafter referred to as “cured layer”) also functions as a part of the insulating layer of the printed wiring board. The portion constituting the insulating layer other than the cured layer is expressed as “insulating resin layer” and is distinguished from the cured layer.

  The reason why the thermosetting resin composition of the present invention can achieve the above-mentioned object has not been clarified in detail at present, but the present inventors presume as follows. However, the factor is not limited to this.

  Polyamideimide is generally known as a compound having high adhesive strength with a conductor. Therefore, when polyamide imide is used as the material of the thermosetting resin composition for forming the adhesive layer, peeling between the conductor layer (metal foil) of the printed wiring board and the cured layer obtained by curing the adhesive layer. Strength is improved. However, polyamideimide has low compatibility and extremely low reactivity with low dielectric constant resins such as the above-mentioned vinyl curing type and allyl curing type. For this reason, a cured layer made of only polyamideimide cannot exhibit sufficient peel strength between the layer using these resins (insulating resin layer).

  In the printed wiring board formed using the thermosetting resin composition of the present invention, the (B) component, or the (C) component and the (D) component enhance the compatibility with the low dielectric constant resin. Furthermore, the polyamideimide as component (A) undergoes a crosslinking reaction by radical polymerization with a low dielectric constant resin that is a constituent material of the adjacent insulating resin layer simultaneously with the polymerization reaction in the adhesive layer. Thereby, the hardened layer obtained from the adhesive layer and the insulating resin layer are almost integrated. As a result, the hardened layer not only has a sufficiently high adhesive force with the conductor layer, but can also improve the breaking strength inside the hardened layer and in the vicinity of the interface between the hardened layer and the insulating resin layer. Even with the resin layer, it has a sufficiently high adhesive force. In addition, due to the improvement in breaking strength, the printed wiring board tends to increase heat resistance.

  In the thermosetting resin composition, the component (A) preferably has a structural unit composed of a saturated hydrocarbon. A printed wiring board formed using such a thermosetting resin composition can further increase the adhesion between the conductor layer and the insulating layer, and can maintain a high adhesion even during moisture absorption. Heat resistance can be expressed.

In the thermosetting resin composition, from the viewpoint of further improving curability, the component (B) preferably has an oxirane ring represented by the following formula (I) or an oxetane ring represented by the following formula (II). More preferably, it has an oxirane ring.

In the thermosetting resin composition, (B) as a functional group having an ethylenically unsaturated bond in the component, a vinyl group, an allyl group, acrylic group _(CH 2 = CHCOO-) and a methacrylic group _{(CH 2 =} CCH 3 COO It is preferable to have one or more groups selected from the group consisting of-).

  From the same viewpoint, the component (C) preferably has two or more oxirane rings or oxetane rings, and more preferably has two or more oxirane rings.

In the above thermosetting resin composition, when the component (B) is an epoxy compound having a polybutadiene structure and an oxirane ring, that is, an epoxy compound having an oxirane ring and further having a polybutadiene structure, the curable further composition is further improved. From the viewpoint of improvement and compatibility from the insulating resin layer, it is preferable. Such component (B) is, for example, from the group consisting of phenolic hydroxyl groups, alcoholic hydroxyl groups, carboxyl groups, amide groups, amino groups, imino groups (—NH—) and groups represented by the following formula (III). It can be obtained by reacting a modified polybutadiene having one or more selected groups with a compound having two or more oxirane rings.

  In the said thermosetting resin composition, it is preferable that the epoxy compound in a thermosetting resin composition has a vinyl group in the side chain and / or the terminal.

Moreover, it is preferable that the said epoxy compound is what has a structural unit represented by the following general formula (1), (2) or (3), or the following general formula (5).
In formula (1), n shows the integer of 2-8, and the sum total of n and m shows the integer of 10-10000. In Formula (2), R ¹ and R ² each independently represent a hydrogen atom or a hydroxyl group, and R ³ represents an acrylic group or an oxiranyl group. In the formula (3), ^{R 4} is a group represented by the following formula (4), i is an integer of 0 to 100, the sum of i and j is an integer of 10 to 10,000.
In formula (5), p represents an integer of 1 to 10,000, q represents an integer of 1 to 100, r and s each independently represent an integer of 0 to 100, and t represents an integer of 1 to 10,000. . However, either r or s represents an integer of 1 or more.

  In the thermosetting resin composition, the component (D) has a vinyl group at its side chain or terminal, and has a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, and the above It is preferably a modified polybutadiene having one or more groups selected from the group consisting of groups represented by formula (III). Here, the “modified polybutadiene” refers to a polybutadiene having a part of the structure of the polybutadiene added with another atom or functional group, or a part of the structure of the polybutadiene substituted with another atom or functional group.

  In the said thermosetting resin composition, the compounding ratio of (B) component is 5 mass parts-200 mass parts with respect to 100 mass parts of (A) component from a viewpoint of exhibiting the effect of the above-mentioned this invention further. And preferably, the total blending ratio of the component (C) and the component (D) is 5 to 200 parts by weight with respect to 100 parts by weight of the component (A), and the blending ratio of the component (D) is (C). It is preferable that it is 5 mass parts-1000 mass parts with respect to 100 mass parts of components.

  Moreover, the resin varnish of the present invention is obtained by dissolving or dispersing the above-described thermosetting resin composition in a solvent. The adhesive layer described above can be formed relatively easily by volatilizing the solvent after applying this resin varnish on the main surface of the conductor layer. Moreover, it is possible to set it as a desired film thickness by providing a suitable amount of resin varnish to a conductor layer according to a use. By forming an adhesive layer from the resin varnish in this way, even if a metal foil having a low surface roughness such as a low profile foil and the above-mentioned dielectric material are used in combination, the metal foil is sufficiently high. Strength can be secured. Therefore, when the resin varnish of the present invention is used, it is possible to sufficiently reduce transmission loss in a high frequency band and to form a printed wiring board with sufficiently strong adhesive force between the insulating layer and the conductor layer. Therefore, the resin varnish of the present invention is suitably used for connecting the conductor layer and the insulating layer of the printed wiring board.

  According to the present invention, it is possible to provide a thermosetting resin composition and a resin varnish that can sufficiently reduce transmission loss, particularly in a high frequency band, and that has a sufficiently strong adhesive force between an insulating layer and a conductor layer. .

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  The thermosetting resin composition according to the preferred first embodiment of the present invention has (A) component; polyamideimide, and (B) component; a functional group capable of reacting with the amide group of the polyamideimide, And a compound having an ethylenically unsaturated bond (hereinafter referred to as “amide-reactive unsaturated compound” as necessary). Hereinafter, the components of the thermosetting resin composition will be described.

((A) component)
The polyamideimide as the component (A) is not particularly limited, and examples thereof include polyamideimide synthesized by a so-called isocyanate method by reaction between trimellitic anhydride and aromatic diisocyanate. As a specific example of the isocyanate method for synthesizing polyamideimide, a method in which an aromatic tricarboxylic acid anhydride and a diamine compound having an ether bond are reacted in the presence of an excess of a diamine compound and then a diisocyanate is reacted (for example, Japanese Patent No. 2897186). And a method of reacting an aromatic diamine compound and trimellitic anhydride (for example, a method described in JP-A No. 04-182466).

  A siloxane structure may be introduced into the main chain of polyamideimide. Thereby, the characteristics such as the elastic modulus and flexibility of the cured layer obtained by curing the adhesive layer are improved, and the drying efficiency and the like can be further improved. Polyamideimide having a siloxane structure in the main chain can be synthesized according to the isocyanate method. Specific examples of the synthesis method include a method of polycondensing an aromatic tricarboxylic acid anhydride, an aromatic diisocyanate and a siloxane diamine compound (for example, a method described in JP-A No. 05-009254), an aromatic dicarboxylic acid or A method of polycondensing an aromatic tricarboxylic acid and a siloxane diamine compound (for example, a method described in JP-A-06-116517), a diamine compound having three or more aromatic rings and a mixture containing siloxane diamine and trimellitic anhydride Examples include a method of reacting a mixture containing diimide dicarboxylic acid obtained by reacting with an acid with an aromatic diisocyanate (for example, a method described in JP-A-06-116517). In this embodiment, even if the polyamideimide synthesized by the above-mentioned known method is used, a sufficiently high metal foil peeling strength can be expressed.

  Furthermore, when a polyamideimide having a structural unit composed of saturated hydrocarbon is used, the peel strength of the metal foil is further improved and the moisture resistance is improved, so that high adhesiveness is maintained even after moisture absorption, and higher moisture resistance. Heat resistance is obtained. From the same viewpoint, the structural unit is more preferably a saturated alicyclic hydrocarbon group. Polyamideimides containing saturated alicyclic hydrocarbon groups are more excellent in moisture and heat resistance and exhibit higher glass transition temperatures (Tg).

  Polyamideimide having a structural unit consisting of a saturated hydrocarbon is, for example, derived from an acid halide derived from an imide group-containing dicarboxylic acid obtained by reacting a diamine compound having a saturated hydrocarbon group with trimellitic anhydride, or It can be obtained by reacting with a diamine compound using a condensing agent. Alternatively, a polyamideimide having a structural unit composed of a saturated hydrocarbon can also be obtained by reacting a diisocyanate with an imide group-containing dicarboxylic acid obtained by reacting a diamine compound having a saturated hydrocarbon group with trimellitic anhydride. It is done. Similarly, the polyamide having a structural unit composed of a saturated alicyclic hydrocarbon may be one having a saturated alicyclic hydrocarbon group as the diamine compound in the above synthesis method.

As said diamine compound, what is represented by the following general formula (6a) or (6b) is mentioned, for example.
In the formulas (6a) and (6b), L ¹ is an optionally halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or the following formula ( A divalent group represented by 7a) or (7b), wherein L ² is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group or a carbonyl group; R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a methyl group optionally substituted with halogen.
In formula (7a), L ³ represents a C 1-3 divalent aliphatic hydrocarbon group, sulfonyl group, oxy group, carbonyl group or single bond which may be halogen-substituted.

  Examples of the diamine compound having a saturated alicyclic hydrocarbon group include 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, bis [4- (3-aminocyclohexyloxy) cyclohexyl] sulfone, and bis [ 4- (4-aminocyclohexyloxy) cyclohexyl] sulfone, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] hexafluoropropane, bis [4- (4-aminocyclohexyloxy) cyclohexyl] methane, 4 , 4′-bis (4-aminocyclohexyloxy) dicyclohexyl, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ether, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ketone, 1,3-bis ( 4-aminocyclohe Siloxy) benzene, 1,4-bis (4-aminocyclohexyloxy) benzene, 2,2′-dimethylbicyclohexyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) dicyclohexyl-4,4 '-Diamine, 2,6,2', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyldicyclohexyl-4,4'-diamine, 3,3 ' -Dihydroxydicyclohexyl-4,4'-diamine, (4,4'-diamino) dicyclohexyl ether, (4,4'-diamino) dicyclohexylsulfone, (4,4'-diaminocyclohexyl) ketone, (3,3'- Diamino) benzophenone, (4,4′-diamino) dicyclohexylmethane, (4,4′-diamino) dicyclohexyl Examples include ether, (3,3′-diamino) dicyclohexyl ether, (4,4′-diamino) dicyclohexyl methane, (3,3′-diamino) dicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) propane and the like. it can. These diamine compounds may be used individually by 1 type, or may be used in combination of 2 or more type. Further, other diamine compounds, that is, diamine compounds having no saturated hydrocarbon group can be used in combination.

  A diamine compound having a saturated alicyclic hydrocarbon group can be easily obtained, for example, by hydrogen reduction of an aromatic diamine compound. Examples of such aromatic diamine compounds include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “BAPP”), bis [4- (3-aminophenoxy). ) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] Methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4 ′ Diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2 , 2′-sulfonylbiphenyl-4,4′-diamine, 3,3′-dihydroxybiphenyl-4,4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, etc. Can be illustrated.

  Hydrogen reduction of an aromatic diamine compound can be performed by a general method for reducing an aromatic ring. Examples of such reduction methods include Raney nickel catalysts and platinum oxide catalysts (D. Varech et al., Tetrahedron Letter 26, 61 (1985), RH Baker et al., J. Am. Chem. Soc., 69, 1250. (1947)), rhodium-aluminum oxide catalyst (JC Sircar et al., J. Org. Chem., 30, 3206 (1965), AI Meyers et al., Organic Synthesis Volume VI, 371 (1988), A. W. Burgstahler, Organic Synthesis Collective Volume V, 591 (1973), A. J. Briggs, Synthesis, 1988, 66), Rozi oxide. -Platinum oxide catalyst (S. Nishimura, Bull. Chem. Soc. Jpn., 34, 32 (1961), EJ Corey et al., J. Am. Chem. Soc. 101, 1608 (1979)), charcoal supported Rhodium catalyst (K. Chebaane et al., Bull. Soc. Chim. Fr., 1975, 244), sodium borohydride-rhodium chloride catalyst (PG Gasman et al., Organic Synthesis Volume VI, 581 (1988), P. G. Gassman et al., Organic Synthesis Collective Volume VI, 601 (1988)) and the like.

The polyamideimide suitably used in the present embodiment can be synthesized by using a diamine compound represented by the following general formula (8) in addition to the diamine compound described above as a diamine compound.
Wherein (8), L ⁴ is methylene group, a sulfonyl group, mosquitoes carbonyl group, a single bond or shows an ether bond, R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an optionally substituted phenyl Represents a group, and k represents an integer of 1 to 50.

R ⁸ and R ⁹ are each independently preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an optionally substituted phenyl group. Examples of the substituent which may be bonded to the phenyl group include an alkyl group having 1 to 3 carbon atoms and a halogen atom. In the diamine compound represented by the general formula (8), L ⁴ is particularly preferably an ether bond from the viewpoint of achieving both a low elastic modulus and a high Tg. Examples of such a diamine compound include Jeffamine D-400, Jeffamine D-2000 (manufactured by Sun Techno Chemical Co., Ltd., trade name), and the like.

  The polyamideimide suitably used in the present embodiment is obtained from a diamine compound having a specific saturated hydrocarbon group as described above, and therefore has higher water absorption resistance or water repellency than conventional polyamideimide. Extremely high. In particular, when the polyamideimide is obtained from a diamine compound having an alicyclic saturated hydrocarbon group and the polyamideimide has a structural unit composed of an alicyclic saturated hydrocarbon, a thermosetting resin composition containing this polyamideimide is used. When used as a layer forming material for a laminate for a printed wiring board, the resulting metal-clad laminate is more hygroscopic than when a resin composition containing a polyamidoimide having an aromatic ring is used for the connection. Adhesiveness is difficult to decrease.

More preferably, the polyamideimide according to the present invention can be synthesized by using an aromatic diamine compound in combination with a diamine compound having a saturated hydrocarbon group. Examples of such aromatic diamine compounds include those represented by the following general formulas (9a) and (9b).
In the formulas (9a) and (9b), L ⁵ is an optionally halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or the following formula ( 10a) or a divalent group represented by (10b), wherein L ⁶ is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group or a carbonyl group R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or a halogen-substituted methyl group.
In formula (10a), L ⁷ represents an optionally substituted divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group or a single bond.

  More specifically, the compound is not particularly limited as long as it is a compound in which two amino groups are directly bonded to an aromatic ring, and a diamine in which two or more aromatic rings are bonded directly or via one group. For example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] Sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) , 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonylbiphenyl-4,4′-diamine, 3,3′-dihydroxybiphenyl- 4,4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4 , 4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like. These aromatic diamine compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Polyamideimide obtained by using these aromatic diamine compounds in combination with the above-mentioned diamine compound further improves Tg and can improve heat resistance.

Furthermore, you may use together the siloxane diamine represented by following General formula (11) as a diamine compound.
In formula (11), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ (hereinafter referred to as “R ^{13 to} R ¹⁸ ”) are each independently represented by 1 to 1 carbon atoms. 3 alkyl groups or optionally substituted phenyl groups are preferred. The substituent that may be bonded to the phenyl group is preferably an alkyl group having 1 to 3 carbon atoms or a halogen atom. R ¹⁹ and R ²⁰ are each independently preferably an alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group, and the arylene group may be an optionally substituted phenylene group or an optionally substituted phenylene group. Good naphthalene groups are preferred. The substituent which may be bonded to the arylene group is preferably an alkyl group having 1 to 3 carbon atoms or a halogen atom. A and b each represent an integer of 1 to 15.

  As such a siloxane diamine, it is particularly preferable to use one having amine groups bonded to both ends of dimethylsiloxane. These siloxane diamines may be used alone or in combination of two or more. Siloxane diamines represented by general formula (11) are silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500), X- 22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd., trade name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) ), (Above, manufactured by Toray Dow Corning Silicone Co., Ltd., trade name) and the like.

  The polyamideimide obtained by using the above-mentioned siloxane diamine as a raw material has a siloxane structure in the main chain, so that the flexibility is improved and the occurrence of swelling and the like under high temperature conditions is greatly reduced. be able to.

  In order to obtain the polyamideimide according to the present embodiment, for example, first, the amino group of the diamine compound is reacted with the carboxyl group or the anhydrous carboxyl group of trimellitic anhydride. At this time, it is preferable that the amino group reacts with an anhydrous carboxyl group. Such a reaction can be carried out at 70 ° C. to 100 ° C. by dissolving or dispersing both compounds in an aprotic polar solvent. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, and cyclohexanone. Of these, NMP is particularly preferable. These aprotic polar solvents may be used alone or in combination of two or more.

  The aprotic polar solvent described above is preferably an amount such that the solid content is 10% by mass to 70% by mass with respect to the total weight of the solution containing the aprotic polar solvent, the diamine compound and tritometic anhydride, The amount is more preferably 20% by mass to 60% by mass. When the solid content in the solution is less than 10% by mass, the amount of the solvent used tends to be industrially disadvantageous, and when it exceeds 70% by mass, the solubility of trimellitic anhydride decreases, It tends to be difficult to perform a sufficient reaction.

  Next, an imide group-containing dicarboxylic acid is obtained by adding an aromatic hydrocarbon that can be azeotroped with water into the solution after the above reaction, and further causing a reaction at 150 ° C. to 200 ° C. to cause a dehydration cyclization reaction. Can do. Examples of aromatic hydrocarbons that can be azeotroped with water include toluene, benzene, xylene, and ethylbenzene, and it is preferable to use toluene. The aromatic hydrocarbon is preferably added in an amount corresponding to 10 to 50 parts by mass with respect to 100 parts by mass of the aprotic polar solvent. When the addition amount of the aromatic hydrocarbon is less than 10 parts by mass with respect to 100 parts by mass of the aprotic polar solvent, the water removal effect tends to be insufficient, and the amount of imide group-containing dicarboxylic acid produced is small. There is a tendency to decrease. Moreover, when it exceeds 50 mass parts, reaction temperature will fall and it exists in the tendency for the production amount of imide group containing dicarboxylic acid to reduce.

  Further, during the dehydration and ring closure reaction, the aromatic hydrocarbon in the solution is distilled off simultaneously with water, so that the amount of the aromatic hydrocarbon may be less than the above preferred range. It is preferable to keep the amount of aromatic hydrocarbons at a constant ratio, for example, by separating the aromatic hydrocarbons distilled in the moisture determination receiver into water and then returning them to the reaction solution. In addition, after completion | finish of a spin-drying | dehydration ring-closing reaction, it is preferable to remove the aromatic hydrocarbon which can azeotrope with water, keeping the temperature of a solution at about 150 to 200 degreeC.

As the imide group-containing dicarboxylic acid obtained as described above, for example, a compound represented by the following general formula (12) is suitable.
In the formula (12), L ⁸ is a residue excluding the amino group of the diamine compound represented by the general formula (6a), (6b), (8), (9a), (9b) or (11). Show. Here, R ^{5 to} R ²⁰ and k, a, and b are as defined above.

  The polyamideimide suitably used in the present embodiment can be produced by inducing an imide group-containing dicarboxylic acid as described above into an acid halide and copolymerizing it with the diamine compound. The imide group-containing dicarboxylic acid is easily derived into an acid halide by reaction with thionyl chloride, phosphorus trichloride, phosphorus pentachloride, or dichloromethyl methyl ether, and the resulting imide group-containing dicarboxylic acid halide is at room temperature or under heating conditions. It can be easily copolymerized with the diamine compound below.

  Moreover, the polyamideimide suitably used in this embodiment can be produced by copolymerizing the imide group-containing dicarboxylic acid as described above with the diamine compound in the presence of a condensing agent. In such a reaction, a general condensing agent that forms an amide bond can be used as the condensing agent, and in particular, dicyclohexylcarbodiimide, diisopropylcarbodiimide, or N-ethyl-N′-3-dimethylaminopropylcarbodiimide alone. Or it is preferable to use together with N-hydroxysuccinimide or 1-hydroxybenzotriazole.

  Furthermore, as described above, the polyamideimide of this embodiment can be obtained by reacting diisocyanate after derivatizing the imide group-containing dicarboxylic acid into an acid halide. When going through such a reaction, (diamine compound: trimellitic anhydride: diisocyanate) is in the range of 1.0: (2.0-2.2) :( 1.0-1.5) in molar ratio. It is preferable that the ratio is in the range of 1.0: (2.0 to 2.2) :( 1.0 to 1.3). In the reaction, by setting the molar ratio of these compounds within the above range, it is possible to obtain a polyamideimide having a higher molecular weight and advantageous for film formation.

As a diisocyanate used in the synthesis | combination of a polyamideimide, the compound represented by following General formula (13) can be illustrated.
In the formula (13), L ⁹ is a divalent organic group having one or more aromatic rings or a divalent aliphatic hydrocarbon group, a group represented by the following formula (14a), It is preferably a group selected from the group consisting of a group represented by 14b), a tolylene group, a naphthylene group, a hexamethylene group and a 2,2,4-trimethylhexamethylene group.

  As the diisocyanate represented by the general formula (13), aliphatic diisocyanate or aromatic diisocyanate can be used, but it is preferable to use aromatic diisocyanate, and it is particularly preferable to use both in combination. Aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. As an example, it is particularly preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the polyamideimide obtained can be improved and the crystallinity can be reduced, so that the film-formability of the polyamideimide can be improved. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  When aromatic diisocyanate and aliphatic diisocyanate are used in combination, it is preferable to add aliphatic diisocyanate in an amount of about 5 to 10 parts by mole with respect to 100 parts by mole of aromatic diisocyanate. Can be further improved.

  The reaction between the imide group-containing dicarboxylic acid and the diisocyanate can be performed at a reaction temperature of 130 ° C. to 200 ° C. by adding the diisocyanate to a solution containing the imide group-containing dicarboxylic acid. In the case of using a basic catalyst, this reaction is preferably carried out at 70 to 180 ° C, more preferably 120 to 150 ° C. When such a reaction is performed in the presence of a basic catalyst, the reaction can proceed at a lower temperature than when the reaction is performed in the absence of a basic catalyst. The progress of side reactions such as reaction between each other can be suppressed, and a high molecular weight polyamideimide compound can be obtained.

  Examples of such basic catalysts include trialkylamines such as trimethylamine, triethylamine, tripropylamine, tri (2-ethylhexyl) amine, and trioctylamine. Among these, triethylamine is particularly preferable because it is a suitable basic catalyst capable of promoting the above-described reaction and can be easily removed from the system after the reaction.

The polyamideimide obtained by the above reaction has a structural unit represented by the following general formula (15). In the formula, L ⁸ and L ⁹ have the same meanings as L ⁸ and L ⁹ described above.

  The weight average molecular weight (Mw) of the polyamideimide obtained as described above is preferably 20000 to 300000, more preferably 30000 to 200000, and particularly preferably 40000 to 150,000. In addition, Mw here is measured by gel permeation chromatography and converted by a calibration curve created using standard polystyrene.

((B) component)
The amide-reactive unsaturated compound (B) has a functional group that can react with the amide group of the polyamide-imide (A) by applying heat or the like, and has an ethylenically unsaturated bond. If it does, it will not specifically limit. Specific examples include an epoxy compound having an ethylenically unsaturated bond, an oxetane compound having an ethylenically unsaturated bond, and the like, and an epoxy compound having an ethylenically unsaturated bond is preferably used.

  The epoxy compound having such an ethylenically unsaturated bond is not particularly limited as long as it is an epoxy resin having one or more ethylenically unsaturated groups such as a vinyl group, an allyl group, an acrylic group, and a methacryl group. Specifically, a polybutadiene-modified epoxy compound having an ethylenically unsaturated group, an alicyclic epoxy resin having a vinyl group such as 1,2-epoxy-4-vinylcyclohexane, glycidyl methacrylate (GMA), methyl glycidyl methacrylate (M -GMA), 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and other epoxy compounds having an acrylic group or a methacryl group. Among these, a polybutadiene-modified epoxy compound having an ethylenically unsaturated group is preferably used.

  Examples of the polybutadiene-modified epoxy compound include a polybutadiene-modified epoxy compound obtained by epoxidizing a part of an ethylenically unsaturated group of a compound having a 1,2-polybutadiene structure and / or a 1,4-polybutadiene structure (hereinafter referred to as “ A first modified epoxy compound "), or a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, or a group represented by the above formula (III), which reacts with an oxirane ring. And a polybutadiene-modified epoxy compound (hereinafter referred to as “second modified epoxy compound”) obtained by reacting a modified polybutadiene having the above group with a polyfunctional epoxy compound having two or more oxirane rings. Among such compounds, it is particularly preferable to use a polybutadiene-modified epoxy compound having one or more vinyl groups at the terminal and / or side chain in the molecule.

  Specific examples of the first modified epoxy compound include a compound represented by the general formula (1) or (2) or a compound having a structural unit represented by the general formula (5). Examples of the epoxy compound represented by the formula (1) include BF-1000 (trade name, manufactured by Nippon Soda Co., Ltd.). Examples of the epoxy compound represented by the formula (2) include PB3600 (trade name, manufactured by Daicel Chemical Industries, Ltd.). As the epoxy compound having the structural unit represented by the formula (5), A1005, A1010, A1020 (above, manufactured by Daicel Chemical Industries, Ltd., trade name) and the like are commercially available.

  Specific examples of the second modified epoxy compound include an epoxy compound obtained by reacting a polybutadiene having a carboxyl group and a bisphenol A type epoxy resin as represented by the general formula (3). As such a second modified epoxy compound, EPB-13 (trade name, manufactured by Nippon Soda Co., Ltd.) is commercially available.

  The second modified epoxy compound is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a brominated bisphenol A type epoxy resin, a biphenyl type epoxy resin or a phenol novolac type as a polyfunctional epoxy compound. Epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene skeleton containing epoxy resin, aralkylene skeleton containing epoxy resin, biphenyl-aralkylene skeleton epoxy resin, phenol salicylaldehyde novolak type epoxy resin , Lower alkyl group-substituted phenol salicylaldehyde novolak type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, polyfunctional glycidyl Amine type epoxy resin and a polyfunctional alicyclic epoxy resin may be a polybutadiene-modified epoxy compound obtained by using the.

  Moreover, the amide reactive unsaturated compound which concerns on this embodiment may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the thermosetting resin composition according to the present embodiment, the blending ratio of the component (B) is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component (A), and 7 parts by mass to 7 parts by mass. It is more preferable to set it as 80 mass parts, and it is still more preferable to set it as 10 mass parts-50 mass parts. When the blending ratio of the amide-reactive unsaturated compound as the component (B) is less than 5 parts by mass, in the printed wiring board obtained by employing the blending component (B), the thermosetting property of the adhesive layer and Since the reactivity between the adhesive layer (cured layer) and the insulating resin layer decreases, the heat resistance, chemical resistance and fracture strength near the interface between the adhesive layer (cured layer) and the insulating resin layer and the adhesive layer (cured layer) Tend to decrease. Moreover, when it exceeds 200 mass parts, it exists in the tendency for the toughness of a hardened layer and the adhesiveness of a hardened layer and metal foil (conductor layer) to fall.

  The thermosetting resin composition of the present embodiment comprises a curing accelerator having a catalytic function that promotes the reaction between the amide group of the polyamideimide (A) and the amide-reactive unsaturated compound (B). Furthermore, it is preferable to contain. Specifically, examples of the curing accelerator include amine compounds, imidazole compounds, organic phosphorus compounds, alkali metal compounds, alkaline earth metal compounds, quaternary ammonium salts, and the like, but are not limited thereto. Moreover, these hardening accelerators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending ratio of the curing accelerator in the thermosetting resin composition according to the present embodiment can be determined according to the blending ratio of the amide-reactive unsaturated compound that is the component (B), and the component (B) 100 It is preferable to set it as 0.05 mass part-10 mass parts with respect to a mass part. When a curing accelerator is blended within this numerical range, an appropriate reaction rate is obtained, and the thermosetting resin composition of the adhesive layer becomes more excellent in reactivity and curability. It has better chemical resistance, heat resistance and / or moisture heat resistance.

  In addition, the thermosetting resin composition according to the present embodiment is a printed wiring board formed using the crosslinking reaction between the components (B) in the adhesive layer and the thermosetting resin composition according to the present embodiment. In order to promote the crosslinking reaction between the compound having an unsaturated bond in the insulating resin layer adjacent to the adhesive layer (cured layer) and the component (B) in the adhesive layer, the component (E); a radical polymerization initiator Furthermore, it is preferable to contain. When a radical polymerization initiator is further contained, a cured layer can be formed more quickly, and the storage stability of the adhesive layer portion tends to be improved.

  Specifically, as a radical polymerization initiator, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2, 5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, di-t-butyl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl- 2,5-bis (t-butylperoxy) hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (T-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, bis (t -Butylperoxy) isophthalate, isobutyryl peroxide, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilyl peroxide and other peroxides, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Examples include, but are not limited to, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzoin methyl ether, methyl-o-benzoylbenzoate, and the like. Moreover, these radical polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

  The blending ratio of the radical polymerization initiator in the thermosetting resin composition according to the present embodiment can be determined according to the blending ratio of the component (B), and is 0 with respect to 100 parts by weight of the component (B). It is preferable to set it as 0.5 mass part-10 mass parts. When a radical polymerization initiator is blended within this numerical range, an appropriate reaction rate can be obtained, and the thermosetting resin composition of the adhesive layer becomes more excellent in reactivity and curability. The breaking strength and the conductor peeling strength are increased, and the chemical resistance, heat resistance and moisture heat resistance are improved.

  In addition, the thermosetting resin composition according to the present embodiment has various additives such as a flame retardant and a filler as necessary, such as heat resistance, adhesiveness, moisture absorption resistance, etc. when used as a printed wiring board. You may mix | blend further with the compounding quantity of the range which does not deteriorate a characteristic.

  Although it does not specifically limit as said flame retardant, Flame retardants, such as a bromine type | system | group, a phosphorus type | system | group, and a metal hydroxide, are used suitably. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl). , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromide Bisphenol A dimethacrylate, unsaturated double bonds brominated reactive flame retardants containing such pentabromobenzylacrylate and brominated styrene.

  Phosphorus flame retardants include aromatic phosphorus such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate) Acid esters, phosphonic acid esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10- Phosphinates such as phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, phosphorus-based flame retardant ammonium polyphosphate and red phosphorus and the like. Examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide.

  The above flame retardants may be used alone or in combination of two or more.

  The blending ratio of the flame retardant in the thermosetting resin composition according to the present embodiment is not particularly limited, but is 5 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). -150 parts by mass, preferably 5-80 parts by mass, more preferably 5-60 parts by mass. If the blending ratio of the flame retardant is less than 5 parts by mass, the flame resistance tends to be insufficient, and if it exceeds 100 parts by mass, the heat resistance of the cured adhesive layer tends to decrease.

  The above-mentioned filler is not particularly limited, but usually an inorganic filler is preferably used. Examples of the inorganic filler include alumina, titanium oxide, mica, silica, beryllia, barium titanate, titanate. Potassium, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, baked clay clay, talc, Examples thereof include aluminum borate, aluminum borate, and silicon carbide. These fillers may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, there is no restriction | limiting in particular also about the shape of a filler, and a particle size, Usually, a particle size of 0.01 micrometer-50 micrometers, Preferably 0.1 micrometer-15 micrometers are used suitably.

  The blending ratio of the filler in the thermosetting resin composition according to the present embodiment is not particularly limited, but 1 part by mass to 100 parts by mass of the total amount of the component (A) and the component (B). 1000 parts by mass is preferable, and 1 part by mass to 800 parts by mass is more preferable.

  In the thermosetting resin composition according to the present embodiment, the component (A), the component (B), a curing accelerator, a radical polymerization initiator and other additives as necessary are blended and mixed by a known method. Can be manufactured.

  The thermosetting resin composition according to the second preferred embodiment of the present invention comprises (A) component; polyamideimide, and (C) component; two or more functional groups capable of reacting with the amide group of the polyamideimide. A compound having a functional group capable of reacting with the component (D); the component (C) and having an ethylenically unsaturated bond (hereinafter referred to as “amide-reactive compound” if necessary) And a “reactive unsaturated compound” as required.) And a curable resin composition. Hereinafter, the curable resin composition constituting the adhesive layer and its components will be described.

  As (A) component which concerns on this embodiment, the thing similar to (A) component which concerns on the suitable 1st Embodiment of this invention can be used.

((C) component)
The amide-reactive compound as the component (C) is not particularly limited as long as it has two or more functional groups that can react with the amide group of the polyamideimide as the component (A) by applying heat or the like. Specific examples include compounds having two or more oxirane rings or oxetane rings, that is, polyfunctional epoxy compounds (oxirane compounds) or oxetane compounds, and polyfunctional epoxy compounds are more preferred. Polyfunctional epoxy compounds include bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolak type Epoxy resin, bisphenol A novolac epoxy resin, naphthalene skeleton-containing epoxy resin, aralkylene skeleton-containing epoxy resin, biphenyl-aralkylene skeleton epoxy resin, phenol salicylaldehyde novolak epoxy resin, lower alkyl group-substituted phenol salicylaldehyde novolak epoxy resin, di Examples include cyclopentadiene skeleton-containing epoxy resins, polyfunctional glycidylamine type epoxy resins, and polyfunctional alicyclic epoxy resins. That. As the component (C), the amide reactive compound may be used alone or in combination of two or more.

((D) component)
The reactive unsaturated compound as component (D) has one or more ethylenically unsaturated bonds in the molecule, and is functionally reactive with the amide reactive compound as component (C) by applying heat or the like. If it is a compound which has group, it will not specifically limit. Specifically, for example, it has an ethylenically unsaturated bond and also has a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, or a group represented by the above formula (III). Examples include modified polybutadiene. In particular, modified polybutadiene in which an ethylenically unsaturated group is a vinyl group present at the terminal and / or side chain is preferably used.

Specific examples of such modified polybutadiene include compounds represented by the following general formula (16), (17), (19) or (21).
In formula (16), R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, c and d each independently represents an integer of 0 to 100, and either c or d is an integer of 1 or more. E represents an integer of 1 to 1000.

In the formula (17), R ²² represents a hydroxyethyl group, a carboxyl group or a group represented by the following general formula (18), f represents an integer of 0 to 100, and the sum of f and g is 10 to 10,000. Indicates an integer.
In the formula (18), R ²³ represents a hydrogen atom or a methyl group.

In the formula (19), R ²⁴ represents a group represented by the following general formula (20a) or (20b), v, w and x each independently represent an integer of 0 to 100, and any of v and w Or represents an integer of 1 or more, and h represents an integer of 1 to 10,000.
In formulas (20a) and (20b), R ²⁵ and R ²⁶ are a single bond, a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted phenylene group, a sulfonyl group, an oxy group, or A carbonyl group is shown.

In formula (21), y represents an integer of 1 to 8, and the sum of y and z represents an integer of 10 to 10,000.

  Examples of the modified polybutadiene represented by the general formula (16) include PP700-300, PP1000-180, PP1000-240 (above, trade name, manufactured by Shin Nippon Petrochemical Co., Ltd.) and the like, which are represented by the general formula (17). Examples of the polybutadiene include G-1000, G-2000, G-3000, C-1000, TEA-1000, TEA-2000 (above, Nippon Soda Co., Ltd., trade name) and other modified compounds represented by the general formula (19). As the polybutadiene, ATBN1300 (manufactured by Ube Industries, trade name) and the like, and as the modified polybutadiene represented by the general formula (21), BN-1015 (manufactured by Nippon Soda Co., Ltd., trade name) are commercially available. is there. Moreover, the reactive unsaturated compound of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type.

  The total blending ratio of the component (C) and the component (D) in the thermosetting resin composition according to this embodiment is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component (A). The amount is more preferably from 80 parts by weight to 80 parts by weight, and even more preferably from 50 parts by weight to 50 parts by weight. In the printed wiring board obtained by adopting the (C) component and the (D) component having such a blending ratio, the total blending ratio of the (C) component and the (D) component is less than 5 parts by mass. Heat resistance and chemical resistance near the interface between the adhesive layer (cured layer) or the insulating resin layer and the adhesive layer (cured layer) because thermosetting and reactivity between the adhesive layer (cured layer) and the insulating resin layer are reduced. Tend to be reduced in strength and breaking strength. Moreover, when it exceeds 200 mass parts, it exists in the tendency for the toughness of a hardened layer and the adhesiveness of a hardened layer and metal foil (conductor layer) to fall.

  Moreover, it is preferable to make the mixture ratio of (D) component into the range of 5 mass parts-1000 weight parts with respect to 100 mass parts of (C) component, and it is more preferable to set it as 20 mass parts-500 mass parts. 50 parts by mass to 150 parts by mass is more preferable. When the blending ratio of component (D) is less than 5 parts by mass, the printed wiring board obtained by employing the blending ratio of component (D) has a reactivity between the adhesive layer (cured layer) and the insulating resin layer. Therefore, the heat resistance and fracture strength in the vicinity of the interface between the insulating resin layer and the adhesive layer (cured layer) tend to decrease. Moreover, when it exceeds 1000 mass parts, there exists a tendency for the thermosetting property of a contact bonding layer to fall, and for the heat resistance and chemical resistance of a contact bonding layer (hardening layer) to fall.

  The thermosetting resin composition of the present embodiment includes a reaction between the amide group of the polyamideimide as the component (A) and the amide reactive compound as the component (C) and the amide reactive group as the component (C) and the component (D). It is preferable to further contain a curing accelerator having a catalytic function that promotes the curing reaction. Specific examples of the curing accelerator include those exemplified and listed in the first embodiment, and these may be used alone or in combination of two or more.

  The thermosetting resin composition according to the present embodiment preferably further contains (E) component; a radical polymerization initiator in order to promote the crosslinking reaction of the unsaturated bond group of component (D). . Specific examples of the radical polymerization initiator include those listed and exemplified in the first embodiment, and these may be used alone or in combination of two or more.

  In the thermosetting resin composition of the present embodiment, the blending ratio of the curing accelerator depends on the blending ratio of the component (C), and the blending ratio of the radical polymerization initiator depends on the blending ratio of the component (D), Each can be determined, and it is preferable from the same viewpoint that the numerical range is the same as the blending ratio with respect to the component (B) in the first embodiment.

  In addition, the thermosetting resin composition according to the present embodiment has various additives such as a flame retardant and a filler as necessary, such as heat resistance, adhesiveness, moisture absorption resistance, etc. when used as a printed wiring board. You may mix | blend further with the compounding quantity of the range which does not deteriorate a characteristic. Specific examples, shapes, and particle sizes of these additives are the same as those described in the first embodiment. Further, the preferable blending ratio is blended with respect to the total amount of the (A) component and the (B) component described in the first embodiment with respect to the total amount of the (A) component, the (C) component, and the (D) component. The numerical range is similar to the ratio.

  A thermosetting resin composition that is a constituent material of an adhesive layer according to a preferred embodiment of the present invention includes (A) component, (C) component, (D) component, a curing accelerator, a radical polymerization initiator, and Accordingly, other additives can be produced by blending and mixing by a known method.

  When the thermosetting resin composition according to a preferred embodiment of the present invention is used as an adhesive layer, the thickness (thickness) of the adhesive layer is preferably 0.1 μm to 10.0 μm, and preferably 0.5 μm to 5 μm. More preferably, it is 0.0 μm. If the film thickness is less than 0.1 μm, it tends to be difficult to improve the peeling strength of the metal foil in the metal-clad laminate provided with the adhesive layer. If it exceeds 10.0 μm, the insulation of the metal-clad laminate is particularly difficult. When a resin as will be described later is used for the resin layer, the high-frequency transmission characteristics tend to deteriorate.

  Moreover, the resin varnish of the present invention can be obtained by dissolving or dispersing the thermosetting resin compositions according to the first and second embodiments described above in a solvent. This resin varnish is applied on the main surface of the conductor layer, and the solvent contained in the resin varnish is volatilized, whereby the adhesive layer can be formed relatively easily. Moreover, it is possible to form a hardened layer having a desired film thickness by applying an appropriate amount of resin varnish to the conductor layer according to the application.

  The solvent used when varnishing the thermosetting resin composition described above is not particularly limited, but specific examples include alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether. , Ethers such as carbitol and butyl carbitol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and mesitylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate And solvents such as esters such as ethyl acetate, nitrogen-containing compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among these solvents, the blending ratio when using aromatic hydrocarbons and ketones is preferably 30 to 300 parts by mass of ketones with respect to 100 parts by mass of aromatic hydrocarbons, and 30 parts by mass. Part to 250 parts by mass, and more preferably 30 parts to 220 parts by mass. Moreover, when varnishing, it is preferable to adjust the amount of the solvent used so that the solid content (nonvolatile content) concentration in the varnish is usually 5% by mass to 80% by mass, but the resin varnish of the present invention is used. When producing a printed wiring board, the solid content concentration and the varnish viscosity can be adjusted by adjusting the amount of the solvent so that the adhesive layer has a desired film thickness, particularly the above-described preferable film thickness.

  The thermosetting resin composition which concerns on 1st and 2nd embodiment mentioned above can be used for the use shown below. For example, a metal foil with an adhesive resin in which the thermosetting resin composition is applied to one side of a metal foil, a metal foil and an insulating resin layer using any resin for the metal foil with an adhesive resin and the insulating resin layer A metal-clad laminate with an adhesive layer provided with an adhesive layer between them, an inner layer plate with a resin for inner layer treatment in which the above-mentioned thermosetting resin composition is applied onto a substrate processed by etching a metal foil, or these A printed wiring board using

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  For example, the thermosetting resin composition of the present invention can be used as it is for an insulating resin layer as well as the above-mentioned adhesive layer, and a prepreg, a resin film, and a metal-clad laminate and a printed wiring board using these can be used. It can be produced by a known method.

  Next, the manufacturing method of the printed wiring board using the thermosetting resin or resin varnish of the present invention will be described step by step.

(Manufacture of metal foil with adhesive layer)
First, when manufacturing a printed wiring board, what gave the adhesive layer to metal foil (henceforth "metal foil with an adhesive layer") is manufactured. The metal foil with an adhesive layer can be produced by a known method. That is, after applying the thermosetting resin composition or resin varnish of the present invention described above to one side (M side) of a metal foil, it is dried and semi-cured (B-stage) to form an adhesive layer on the metal foil. To do. Thereby, metal foil with an adhesive layer can be obtained. Application | coating can be implemented by a well-known method, for example, can be performed using a kiss coater, a roll coater, a comma coater, etc. The drying may be performed in a heat drying oven or the like, usually at a temperature of 70 ° C. to 250 ° C., preferably 100 ° C. to 200 ° C. for 1 minute to 30 minutes, preferably 3 minutes to 15 minutes. The drying temperature at this time is preferably equal to or higher than the temperature at which the solvent can be volatilized when a solvent is used to dissolve the thermosetting resin composition.

  As shown in the partial perspective view of FIG. 1, the metal foil with an adhesive layer obtained in this way has a structure in which an adhesive layer 20 is laminated on the M surface 12 of the metal foil 10 described above.

  Although the said metal foil is not specifically limited, Although copper foil, nickel foil, and aluminum foil are mentioned, Usually, it is preferable when electric field copper foil or rolled copper foil is used. In addition, this metal foil improves the barrier layer formation treatment with nickel, tin, zinc, chromium, molybdenum, cobalt, etc., and adhesion with the insulating layer from the viewpoint of improving its rust resistance, chemical resistance and heat resistance. Therefore, it is preferable that a normal surface treatment such as a surface roughening treatment or a treatment with a silane coupling agent is performed.

  Among these surface treatments, regarding the surface roughening treatment, if the roughening treatment is performed so that the surface roughness (Rz) on the M-plane is preferably 4 μm or less, more preferably 2 μm or less, high-frequency transmission characteristics are obtained. This can be further improved. The surface roughness Rz is a ten-point average roughness based on JIS-B0601-1994. Examples of the silane coupling agent used for the silane coupling agent treatment include epoxy silane, amino silane, cationic silane, vinyl silane, acryloxy silane, methacryloxy silane, ureido silane, mercapto silane, sulfide silane, and isocyanate silane. However, it is not particularly limited.

  The metal foil may be a single layer made of one kind of metal material, may be a single layer made of a plurality of metal materials, or may be formed by laminating a plurality of metal layers of different materials, The thickness is not particularly limited. Among these metal foils, as copper foil, F2-WS (Furukawa Circuit Foil, Rz = 3.0), F0-WS (Furukawa Circuit Foil, trade name, Rz = 1.2 μm), 3EC- VLP (manufactured by Mitsui Kinzoku Co., Ltd., trade name, Rz = 3.0) is commercially available.

(Manufacture of metal-clad laminates)
Next, a metal-clad laminate is manufactured using the metal foil with an adhesive layer. The metal-clad laminate may be formed using a metal foil with an adhesive layer, and the formation method, shape, laminated state, etc. are not particularly limited. Therefore, the metal-clad laminate is laminated, for example, such that the above-mentioned metal foil with an adhesive layer is in contact with at least one surface of an insulating resin film containing an insulating resin so that the adhesive layer of the metal foil with an adhesive layer is in contact with it. Thus, a laminate is obtained, and the laminate is obtained by heating and pressing. More specifically, first, a prepreg is prepared as an insulating resin film for forming a substrate for a printed wiring board. As the prepreg, those prepared by a known method by impregnating a reinforcing fiber such as glass fiber or organic fiber with a resin such as polybutadiene, triallyl cyanurate, triallyl isocyanurate, or functionalized polyphenylene ether can be used. .

  Next, a plurality of prepared prepregs are preferably stacked, and the metal foil with the adhesive layer according to the present invention described above is adhered to the prepreg so that the adhesive layer is in contact therewith. A metal-clad laminate is formed by heating and / or pressurizing. The heating in this case can be preferably performed at a temperature of 150 ° C. to 250 ° C., and the pressurization can be preferably performed at a pressure of 0.5 to 10.0 MPa. Heating and pressing are preferably performed simultaneously using a vacuum press or the like. In this case, the adhesive layer (cured layer) and the insulating resin layer are sufficiently cured by performing these treatments for 30 minutes to 10 hours, A metal-clad laminate having excellent adhesion between the conductor layer and the insulating layer and excellent in chemical resistance, heat resistance, and moisture resistance can be produced. The metal foil with an adhesive layer may be applied to only one side of the prepreg, or may be applied to both sides to produce a double-sided metal-clad laminate.

  For example, as shown in the partial cross-sectional view of FIG. 2, the metal-clad laminate manufactured in this way includes a plurality of insulating resin layers 40 that are cured products (base materials) of prepregs, which are cured products of adhesive layers. A certain hardened layer 30 is sandwiched, and a metal foil 10 as a conductor layer is further sandwiched therebetween. Further, the insulating resin layer 40 and the cured layer 30 are substantially integrated by curing, in other words, the conductive layer 10 sandwiches the insulating layer 50 composed of the insulating resin layer 40 and the cured layer 30. It consists of Since such a metal-clad laminate is manufactured using the above-described metal foil with an adhesive layer, it is possible to form a printed wiring board that can sufficiently reduce transmission loss particularly in a high-frequency band, and further, the insulating layer 50 and The adhesive force between the conductor layers 10 is sufficiently strong.

(Manufacture of printed wiring boards)
Next, a printed wiring board is manufactured using the obtained metal-clad laminate. The printed wiring board may be formed using a metal foil with an adhesive layer, and the formation method, shape, laminated state, and the like are not particularly limited. Therefore, the printed wiring board according to the present embodiment is obtained, for example, by subjecting the above-described metal-clad laminate to drilling or metal plating by a known method and then processing the metal foil into a circuit shape by etching. It is done.

  For example, as shown in the partial sectional view of FIG. 3, the printed wiring board obtained in this way has a plating film 60 formed on the wall surface of the through hole 70 and the conductor layer 10, and the conductor layer 10 is formed of a circuit. Forming part.

  Moreover, a multilayer printed wiring board can be formed using this printed wiring board as an inner layer core substrate. First, one or more layers of the above-described prepreg are laminated on one or both sides of the inner layer core substrate that is the printed wiring board, and a metal foil is further arranged on the prepreg layer. Or you may arrange | position the metal foil with an adhesive layer which concerns on this invention on the layer of a prepreg so that an adhesive layer may contact | connect a prepreg. Then, the obtained laminate can be heat-pressed and subjected to drilling or metal plating, and then the outermost metal foil can be processed into a circuit shape to obtain a multilayer printed wiring board.

  Furthermore, by using a plurality of inner-layer core substrates and a plurality of the above-mentioned prepregs, these are alternately laminated, heated and pressed, and subjected to the same process as described above, thereby further producing a multilayer printed wiring board. Obtainable. As the outermost layer of the multilayer printed wiring board, a normal metal foil or a metal foil with an adhesive of the present invention may be used on the prepreg layer, or a core substrate may be used.

  The printed wiring board manufactured using the thermosetting resin composition according to the preferred embodiment of the present invention described above includes polybutadiene, triallyl cyanurate, triallyl isocyanurate, functionalization as a constituent material of the insulating resin layer. When a low dielectric constant resin such as polyphenylene ether is employed, not only can the high foil peel strength be exhibited, but also high adhesive strength can be maintained during moisture absorption. As a result, the metal-clad laminate has sufficiently high heat resistance and moisture heat resistance.

  Furthermore, these excellent characteristics are sufficiently expressed even when a metal foil having a relatively small surface roughness of the adhesive surface is provided, so that excellent high frequency characteristics and high adhesiveness and heat resistance. Coexistence is possible. For these reasons, the use of the thermosetting resin composition of the present invention is effective as a printed wiring board used in various electric / electronic devices that handle high-frequency signals.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Synthesis of Polyamideimide]
(Synthesis Example 1)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, (4,4′-diamino) dicyclohexylmethane (Wandamine HM (as diamine compound A having a saturated alicyclic hydrocarbon group) was added. WHM), manufactured by Shin Nippon Chemical Co., Ltd., trade name) 45 mmol, reactive silicone oil as siloxane diamine compound B (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 5 mmol, anhydrous tri 105 mmol of merit acid (TMA) and 145 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 60 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 1 (solid content concentration of 30% by mass) was obtained. It was 50000 when the weight average molecular weight (Mw) of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 2)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, (4,4′-diamino) dicyclohexylmethane (Wandamine HM (as diamine compound A having a saturated alicyclic hydrocarbon group) WHM), manufactured by Shin Nippon Rika Co., Ltd., trade name) 140 mmol, as a diamine compound C having a saturated aliphatic hydrocarbon group, Jeffamine D-2000 (manufactured by Suntechno Chemical Co., trade name) 35 mmol, trimellitic anhydride (TMA) 368 mmol , 413 g of N-methyl-2-pyrrolidone (NMP) was added as an aprotic polar solvent, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 210 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 2 (solid content concentration of 30% by mass) was obtained. It was 64000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 3)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd.) 30 mmol as a diamine compound C having a saturated aliphatic hydrocarbon group. , Reactive silicone oil (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 10 mmol as siloxane diamine compound B, (4,4′-diamino) diphenylmethane ( DDM) 60 mmol, trimellitic anhydride (TMA) 210 mmol, and 407 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 210 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 3 (solid content concentration of 30% by mass) was obtained. It was 62000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 4)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd.) 30 mmol as a diamine compound C having a saturated aliphatic hydrocarbon group. , 120 mmol of (4,4′-diamino) diphenylmethane (DDM) as aromatic diamine compound D, 315 mmol of trimellitic anhydride (TMA), 442 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent, The temperature in the flask was set to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 180 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 4 (solid content concentration of 30% by mass) was obtained. It was 74000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 5)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, a reactive silicone oil (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 11 mmol, (4,4′-diamino) diphenylmethane (DDM) 99 mmol as aromatic diamine compound D, 231 mmol trimellitic anhydride (TMA) 231 mmol, N-methyl-2-pyrrolidone (aprotic polar solvent) (NMP) 309 g was added, the temperature in the flask was set to 80 ° C., and the mixture was stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 132 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 5 (solid content concentration of 30% by mass) was obtained. It was 56000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 6)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, a reactive silicone oil (X-22-161-AS, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 850, trade name) 24 mmol, aromatic diamine compound D (4,4′-diamino) diphenylmethane (DDM) 96 mmol, trimellitic anhydride (TMA) 252 mmol, aprotic polar solvent N-methyl-2-pyrrolidone ( NMP) 289 g was added, and the temperature in the flask was set to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 144 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C., and the mixture was reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 6 (solid content concentration of 30% by mass) was obtained. It was 52000 when Mw of this NMP solution was measured by the gel permeation chromatography.

Table 1 summarizes the amount of each polyamideimide raw material used in Synthesis Examples 1-6.

[Preparation of resin varnish (curable resin composition)]
(Preparation Example 1)
(A) Component (B) 7.5 g of the first modified epoxy compound (PB3600, manufactured by Daicel Chemical Industries, Ltd.), which is the component (B), is added to 100 g of the polyamideimide NMP solution obtained in Synthesis Example 1. Furthermore, 0.08 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) as a curing accelerator, and α, α′-bis (t -Butylperoxy) Diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation, trade name) 0.15 g was added, and then 80 g of N, N-dimethylacetamide was added, and the resin varnish of Preparation Example 1 (for adhesive layer) (Solid content concentration of about 20% by mass) was prepared.

(Preparation Example 2)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 2 as the component (A), the second modified epoxy compound as the component (B) (EPB-13, manufactured by Nippon Soda Co., Ltd., carboxylic acid-terminated polybutadiene and bisphenol A) 6.0 g of a reaction product with a type epoxy resin, trade name), and further, 0.06 g of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd., trade name) as a curing accelerator, (E) After adding 0.12 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator as a component, 75 g of N, N-dimethylacetamide The resin varnish (for the adhesive layer) of Preparation Example 2 (solid content concentration of about 20% by mass) was prepared.

(Preparation Example 3)
Compound (A) 10.0 g of the first modified epoxy compound (A1020, manufactured by Daicel Chemical Industries, Ltd., trade name) as the component (B) is added to 100 g of the polyamideimide NMP solution obtained in Synthesis Example 3 as the component. Furthermore, 0.1 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) is used as a curing accelerator, and α, α′-bis (t -Butylperoxy) Diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation, trade name) 0.2 g was added, and then 90 g of N, N-dimethylacetamide was blended, and the resin varnish of Preparation Example 3 (for adhesive layer) (Solid content concentration of about 20% by mass) was prepared.

(Preparation Example 4)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 4 as the component (A), cresol novolac type epoxy resin (N673, manufactured by Dainippon Ink & Chemicals, trade name) 5.0 g as the component (C), And 4.0 g of modified polybutadiene (BN-1015, Nippon Soda Co., Ltd., trade name) as component (D), and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. , Trade name) 0.05 g, α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator (E) component is 0.08 g. After the addition, 85 g of N, N-dimethylacetamide was blended to prepare a resin varnish (for adhesive layer) of Preparation Example 4 (solid content concentration of about 20% by mass).

(Preparation Example 5)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 5 which is component (A), 5.0 g of phenol novolac epoxy resin (N770, manufactured by Dainippon Ink & Chemicals, Inc.) which is component (C), And 4.0 g of modified polybutadiene (C-1000, manufactured by Nippon Soda Co., Ltd., trade name) as component (D), and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. , Trade name) 0.05 g, α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator (E) component is 0.08 g. After the addition, 85 g of N, N-dimethylacetamide was blended to prepare a resin varnish (for adhesive layer) of Preparation Example 5 (solid content concentration of about 20% by mass).

(Preparation Example 6)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 6 which is component (A), bisphenol A type epoxy resin (DER-331L, manufactured by Dow Chemical Japan, trade name) 6.0 g which is component (C), And 4.0 g of modified polybutadiene (ATBN1300X42, manufactured by Ube Industries, Ltd., trade name) as component (D), and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. Name) 0.06 g, α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation, trade name) 0.08 g was added as a radical polymerization initiator as component (E). Thereafter, 90 g of N, N-dimethylacetamide was blended to prepare a resin varnish (for adhesive layer) of Preparation Example 6 (solid content concentration of about 20% by mass).

(Preparation Example 7)
(B) Component glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., trade name) 5.0 g is blended with 100 g of the polyamideimide NMP solution obtained in Synthesis Example 1 as component (A), and further cured. 2-ethyl-4-methylimidazole (2E4MZ, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.05 g as an accelerator, and α, α′-bis (t-butylperoxy) as a radical polymerization initiator as component (E) ) After adding 0.10 g of diisopropylbenzene (Perbutyl P, manufactured by NOF Corporation, trade name), 70 g of N, N-dimethylacetamide was added, and the resin varnish of Preparation Example 7 (for adhesive layer) (solid content concentration) About 20% by weight).

(Comparative Preparation Example 1)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 1 as the component (A), 7.5 g of a cresol novolac type epoxy resin (N673, manufactured by Dainippon Ink & Chemicals, Inc.) as the component (C) Further, 0.08 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and then 80 g of N, N-dimethylacetamide was added for comparative preparation. The resin varnish (for adhesive layer) of Example 1 (solid content concentration of about 20% by mass) was prepared.

(Comparative Preparation Example 2)
To 100 g of NMP solution of polyamideimide obtained in Synthesis Example 5 which is component (A), 5.0 g of phenol novolac type epoxy resin (N770, manufactured by Dainippon Ink & Chemicals, Inc.) which is component (C). Further, 0.05 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and then 70 g of N, N-dimethylacetamide was added for comparative preparation. The resin varnish (for adhesive layer) of Example 2 (solid content concentration of about 20% by mass) was prepared.

(Comparative Preparation Example 3)
To 100 g of the polyamideimide NMP solution obtained in Synthesis Example 6 as the component (A), 6.0 g of the bisphenol A type epoxy resin (DER-331L, manufactured by Dow Chemical Japan Co., Ltd.) as the component (C). Further, 0.06 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) was added as a curing accelerator, and then 75 g of N, N-dimethylacetamide was added for comparison preparation. The resin varnish (for adhesive layer) of Example 3 (solid content concentration of about 20% by mass) was prepared.

[Production of metal foil with adhesive layer]
The resin varnish (for adhesive layer) obtained in Preparation Examples 1 to 7 and Comparative Preparation Examples 1 to 3 was used as an electrolytic copper foil having a thickness of 12 μm (F0-WS-18, low profile copper foil, manufactured by Furukawa Electric Co., Ltd.). Each of the M surfaces (surface roughness (Rz): 0.8 μm) was naturally cast and then dried at 150 ° C. for 5 minutes, and the metal foils with adhesive layers of Examples 1 to 7 and Comparative Examples 1 to 3 were used. Was made. The thickness of the adhesive layer after drying was 2 μm. The cases where the resin varnishes of Preparation Examples 1 to 7 correspond to Examples 1 to 4, Reference Examples 5, 6 and Example 7 , respectively, and the case where the resin varnishes of Comparative Adjustment Examples 1 to 3 are used. It corresponds to Comparative Examples 1 to 3, respectively.

[Preparation of insulating resin layer prepreg]
(Production Example 1)
First, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 120 g of a polyphenylene ether resin (modified PPO-noryl PKN4752, manufactured by Nippon GE Plastics Co., Ltd., trade name) were placed. The solution was stirred and dissolved while heating the temperature to 90 ° C. Next, 80 g of triallyl isocyanurate (TAIC, Nippon Kasei Kogyo Co., Ltd., trade name) was added to the flask while stirring, and the mixture was cooled to room temperature after confirming that it was dissolved or uniformly dispersed. Next, after adding 2.0 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A resin varnish (for insulating resin layer) having a solid content concentration of about 30% by mass was obtained.

  The obtained resin varnish (for insulating resin layer) was impregnated into glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heat-dried at 120 ° C. for 5 minutes to obtain a resin content of 50 mass. % Of the prepreg for insulating resin layer of Preparation Example 1 was obtained.

(Production Example 2)
First, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 120 g of a polyphenylene ether resin (modified PPO-noryl PKN4752, manufactured by Nippon GE Plastics Co., Ltd., trade name) were placed. The solution was stirred and dissolved while heating the temperature to 90 ° C. Next, while stirring, 80 g of 1,2-polybutadiene (B-1000, manufactured by Nippon Soda Co., Ltd., trade name) and 10 g of divinylbenzene (DVB) as a crosslinking aid were added and dissolved or uniformly dispersed. After confirmation, it was cooled to room temperature. Next, after adding 2.0 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A resin varnish (for insulating resin layer) having a solid content concentration of about 30% by mass was obtained.

  The obtained resin varnish (for insulating resin layer) was impregnated into glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heat-dried at 120 ° C. for 5 minutes to obtain a resin content of 50 mass. % Of the prepreg for insulating resin layer of Preparation Example 1 was obtained.

(Production Example 3)
First, in a 10 L separable flask equipped with a condenser, a thermometer, and a stirrer, 5000 mL of tetrahydrofuran (THF) and 100 g of a polyphenylene ether resin (Noryl PPO646-111, manufactured by Nippon GE Plastics, Inc., trade name) The temperature in the flask was stirred and dissolved while heating to 60 ° C. After returning this to room temperature, 540 mL of n-butyllithium (1.55 mol / L, hexane solution) was added under a nitrogen stream and stirred for 1 hour. Furthermore, after adding 100 g of allyl bromide and stirring for 30 minutes, an appropriate amount of methanol was blended, and the precipitated polymer was isolated to obtain an allylated polyphenylene ether.

  Next, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 100 g of the allylated polyphenylene ether were put and dissolved while stirring while heating the temperature in the flask to 90 ° C. Next, 100 g of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Kogyo Co., Ltd., trade name) was added to the flask while stirring, and the mixture was cooled to room temperature after confirming that it was dissolved or uniformly dispersed. Then, after adding 2.5 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A resin varnish (for insulating resin layer) having a solid content concentration of about 30% by mass was obtained.

  The obtained resin varnish (for insulating resin layer) was impregnated into glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then heat-dried at 120 ° C. for 5 minutes to obtain a resin content of 50 mass. % Of the prepreg for insulating resin layer of Preparation Example 1 was obtained.

[Production of double-sided copper-clad laminate]
The adhesive layers of Examples 1 to 4, 7 and Reference Examples 5 and 6 and Comparative Examples 1 to 3 are formed on both surfaces of the base material obtained by stacking the four prepregs for insulating resin layer of any of Preparation Examples 1 to 3 described above. After attaching the attached metal foil so that the respective adhesive layers are in contact with each other, it was subjected to heat and pressure molding under the press conditions of 200 ° C., 2.9 MPa, and 70 minutes, and Examples 1 to 4, 7 and Reference Example 5 were performed. 6 , Double-sided copper-clad laminates (thickness: 0.55 mm) using the metal foils with adhesive layers of Comparative Examples 1 to 3 were produced. In addition, the metal foil with an adhesive layer of Examples 1 to 4, 7 and Reference Examples 5 and 6 and Comparative Examples 1 to 3, the polyamide imide of Synthesis Examples 1 to 6 and the prepreg for insulating resin layers of Preparation Examples 1 to 3 The combinations are shown in Table 2.

For comparison, an electrolytic copper foil (F0-WS-18, Furukawa Electric Co., Ltd.) having a thickness of 18 μm without an adhesive layer on both surfaces of the base material formed by stacking the four prepregs for insulating resin layer of Production Example 1 Co., Ltd., trade name), or 18 μm thick electrolytic copper foil (GTS-18, general copper foil, manufactured by Furukawa Electric Co., Ltd., surface roughness (Rz): 8 μm , trade name) without an adhesive layer Was applied so that the M surface was in contact with each other, followed by heating and pressing under the press conditions of 200 ° C., 2.9 MPa, and 70 minutes to produce double-sided copper-clad laminates (thickness: 0.55 mm), respectively. did. Among these, the former double-sided copper clad laminate provided with the electrolytic copper foil is related to Comparative Example 4, and the double-sided copper clad laminate provided with the latter electrolytic copper foil is related to Comparative Example 5.

[Measurement of peel strength of copper foil in copper-clad laminate]
An unnecessary copper foil portion was removed by etching so that the copper foil of the obtained copper-clad laminate had a circuit shape with a line width of 5 mm, and a laminate sample having a 2.5 cm × 10 cm planar rectangle was produced. The sample thus prepared was held for 5 hours in a normal and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm, 100% RH), and then peeled off with copper foil (unit: kN / m). ) Was measured under the following conditions.
Test method: 90 ° direction tensile test Tensile speed: 50 mm / min Measuring device: Autograph AG-100C manufactured by Shimadzu Corporation
The obtained results are shown in Table 2. In addition, about this copper foil peeling strength, what was shown by "---" in a table | surface cannot measure the copper foil peeling strength since the copper foil had already peeled after hold | maintaining in PCT. Means that.

[Evaluation of solder heat resistance of copper-clad laminate]
The copper foil on one side of the above-mentioned copper-clad laminate cut to a 50 mm square is etched into a predetermined shape, and the normal time and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm) for a predetermined time ( (1-5 hours) After being held, it was immersed in a molten solder at 260 ° C. for 20 seconds, and the appearance of the obtained copper-clad laminate (3 sheets) was examined visually. The results are shown in Table 2. In addition, the number in a table | surface means the number of sheet | seats by which the generation | occurrence | production of swelling and a measling was not recognized between an insulating layer and copper foil (conductor layer) among three copper clad laminated boards after a solder immersion.

[Evaluation of transmission loss of copper-clad laminate]
The transmission loss (unit: dB / m) of the copper-clad laminate was measured by a triplate line resonator method using a vector network analyzer. Measurement conditions were as follows: line width: 0.6 mm, insulating layer distance between upper and lower ground conductors: about 1.04 mm, line length: 200 mm, characteristic impedance: about 50Ω, frequency: 3 GHz, measurement temperature: 25 ° C. The results are shown in Table 2.

It is a fragmentary perspective view of the metal foil with an adhesive layer which concerns on suitable embodiment of this invention. 1 is a partial cross-sectional view of a metal-clad laminate according to a preferred embodiment of the present invention. It is a fragmentary sectional view of the printed wiring board concerning a suitable embodiment of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Metal foil (conductor layer, circuit), 20 ... Adhesive layer, 30 ... Hardened layer, 40 ... Insulating resin layer (insulating resin film), 50 ... Insulating layer, 60 ... Plating film, 70 ... Through-hole.

Claims (13)

(A) component; polyamideimide,
(B) component; a compound having a functional group capable of reacting with the amide group of the polyamideimide and having an ethylenically unsaturated bond;
(E) component; radical polymerization initiator;
Containing
The component (A) has a structural unit composed of a saturated hydrocarbon, and the structural unit is at least selected from the group consisting of diamine compounds represented by the following general formulas (6a), (6b) and (8), respectively. A thermosetting resin composition, which is a unit derived from one kind of diamine compound.
[In the formulas (6a) and (6b), L ¹ is an optionally substituted divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or the following formula: A divalent group represented by (7a) or (7b), wherein L ² is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group or a carbonyl group; R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a methyl group which may be substituted with a halogen atom. ]
[In Formula (7a), L ³ represents a C 1-3 divalent aliphatic hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group, or a single bond which may be halogen-substituted. ]
[In the formula (8), L ⁴ represents a methylene group, a sulfonyl group, a carbonyl group, a single bond or an ether bond, and R ⁸ and R ⁹ each independently represents a hydrogen atom, an alkyl group or an optionally substituted phenyl. Represents a group, and k represents an integer of 1 to 50. ]   The said (B) component has an oxirane ring or an oxetane ring, The thermosetting resin composition of Claim 1 characterized by the above-mentioned.   2. The functional group having an ethylenically unsaturated bond in the component (B) has at least one group selected from the group consisting of a vinyl group, an allyl group, an acrylic group, and a methacryl group. Or the thermosetting resin composition of 2.   The thermosetting resin composition according to claim 1, wherein the component (B) is an epoxy compound having a polybutadiene structure and an oxirane ring. A modified polybutadiene in which the epoxy compound has one or more groups selected from the group consisting of phenolic hydroxyl groups, alcoholic hydroxyl groups, carboxyl groups, amide groups, amino groups, imino groups, and groups represented by the following formula (III) The thermosetting resin composition according to claim 4, which is a compound obtained by reacting a compound having two or more oxirane rings.
  The thermosetting resin composition according to claim 4 or 5, wherein the epoxy compound has a vinyl group at a side chain and / or a terminal thereof. The epoxy compound is represented by the following general formula (1), (2) or (3) since it expressed also by characterized in that there claim 4 thermosetting resin composition.
[In Formula (1), n shows the integer of 2-8, and the sum total of n and m shows the integer of 10-10000. ]
[In Formula (2), R ¹ and R ² each independently represent a hydrogen atom or a hydroxyl group, and R ³ represents an acrylic group or an oxiranyl group. ]
[In formula (3), R ⁴ represents a group represented by the following formula (4), i represents an integer of 0 to 100, and the sum of i and j represents an integer of 10 to 10,000. ]
  The blending ratio of the component (B) is 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component (A), and thermosetting according to any one of claims 1 to 7. Resin composition. (A) component; polyamideimide,
(C) component; a compound having two or more functional groups capable of reacting with the amide group of the polyamideimide;
(D) component; a compound having a functional group capable of reacting with the component (C) and having an ethylenically unsaturated bond;
(E) component; radical polymerization initiator;
Containing
The component (A) has a structural unit composed of a saturated hydrocarbon, and the structural unit is at least selected from the group consisting of diamine compounds represented by the following general formulas (6a), (6b) and (8), respectively. A thermosetting resin composition, which is a unit derived from one kind of diamine compound.
[In the formulas (6a) and (6b), L ¹ is an optionally substituted divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or the following formula: A divalent group represented by (7a) or (7b), wherein L ² is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group or a carbonyl group; R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a methyl group which may be substituted with a halogen atom. ]
[In Formula (7a), L ³ represents a C 1-3 divalent aliphatic hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group, or a single bond which may be halogen-substituted. ]
[In the formula (8), L ⁴ represents a methylene group, a sulfonyl group, a carbonyl group, a single bond or an ether bond, and R ⁸ and R ⁹ each independently represents a hydrogen atom, an alkyl group or an optionally substituted phenyl. Represents a group, and k represents an integer of 1 to 50. ]   The thermosetting resin composition according to claim 9, wherein the component (C) has two or more oxirane rings or oxetane rings.   The component (D) has a vinyl group at its side chain and / or terminal, and is represented by a phenolic hydroxyl group, an alcoholic hydroxyl group, a carboxyl group, an amide group, an amino group, an imino group, and the above formula (III). The thermosetting resin composition according to claim 9 or 10, which is a modified polybutadiene having one or more groups selected from the group consisting of:   The total blending ratio of the component (C) and the component (D) is 5 to 200 parts by weight with respect to 100 parts by weight of the component (A), and the blending ratio of the component (D) is the above ( It is 5 mass parts-1000 mass parts with respect to 100 mass parts of C) component, The thermosetting resin composition as described in any one of Claims 9-11 characterized by the above-mentioned.   A resin varnish obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 12 in a solvent.