JP2020200454A - Thermosetting resin composition for thermal conductive material and cured product of the same, electronic component and electronic apparatus - Google Patents

Abstract

To provide a thermally conductive thermosetting resin composition and a cured product of the composition having excellent thermal conductivity and dielectric characteristics and high reliability, an electronic component and an electronic apparatus.SOLUTION: A thermosetting resin composition for a thermally conductive material is provided, which comprises a binder component and a thermally conductive filler. The binder component is a binder component (I) containing a styrene-based elastomer (P1) having a carboxylic acid anhydride group and a polyisocyanate component (C1), a binder component (II) containing a polyamide resin (P2) having a phenolic hydroxyl group in a side group and a compound (C2) having three or more functional groups, a binder component (III) containing a specific polyurethane resin (P3) and an epoxy compound (C3), or a binder component (IV) containing a specific polyimide resin (P4) and a compound (C4) having two or more functional groups. The cured product shows a relative permittivity of 4.0 or less and a dielectric loss tangent of 0.010 or less.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting resin composition for a heat conductive material and a cured product thereof. Further, the present invention relates to an electronic component including a cured product of the thermosetting resin composition for a heat conductive material, and an electronic device having the electronic component.

As the density of integrated circuits increases, the amount of heat generated inside electronic devices tends to increase, and there is a demand for a technique for more efficiently diffusing heat generated inside electronic components than ever before. In particular, resin materials are often used inside electronic devices for the purpose of weight reduction, etc., but since the thermal conductivity of resin materials is generally lower than that of metals and ceramics, resins with excellent thermal conductivity The composition is required.

As a heat radiating sheet using a resin, a heat radiating sheet in which a heat conductive filler is dispersed in silicone rubber is known. Further, a heat-resistant elastic material to which a good heat conductive material is added to a silicone polymer precursor (Patent Document 1) and a resin composition containing a specific boron nitride powder (Patent Document 2) have been proposed.

Japanese Unexamined Patent Publication No. 2005-209955 Japanese Unexamined Patent Publication No. 2014-40341

While a resin composition having excellent thermal conductivity is required, the frequency band of signals used for printed wiring boards and the like is shifting from the mega Hz band to the giga Hz band, and the higher the frequency, the more the electric signal is transmitted. Since the loss becomes large, a resin composition having excellent dielectric properties in the high frequency band is required.

The present invention has been made in view of the above background, and provides a highly reliable thermosetting thermosetting resin composition having excellent thermal conductivity and dielectric properties, a cured product thereof, electronic parts, and electronic devices. The purpose.

As a result of diligent studies by the present inventors, they have found that the problems of the present embodiment can be solved in the following aspects, and have completed the present invention.
[1]: A thermosetting resin composition for a heat conductive material containing a binder component containing a thermosetting resin and a curing agent and a heat conductive filler.
The binder component is
A binder component (I) containing a styrene-based elastomer (P1) having an anhydride group of a carboxylic acid and a polyisocyanate component (C1) that reacts with the anhydride group.
A binder component (II) containing a polyamide resin (P2) having a phenolic hydroxyl group as a side group and a trifunctional or higher functional compound (C2) capable of reacting with the phenolic hydroxyl group.
A binder component (III) containing a polyurethane resin (P3) having a carboxyl group and an epoxy compound (C3) capable of reacting with the carboxyl group, or a hydrocarbon having a reactive functional group and having 20 to 60 carbon atoms. A binder component (IV) containing a polyimide resin (P4) containing a group and a bifunctional or higher functional compound (C4) that reacts with the reactive functional group.
The cured product after curing the thermosetting resin composition for the heat conductive material is
The relative permittivity is 4.0 or less at a frequency of 5 GHz and 23 ° C.
Dissipation factor is 0.010 or less at a frequency of 5 GHz and 23 ° C.
Thermosetting resin composition for heat conductive materials.
[2] The styrene-based elastomer (P1) is
It is a block copolymer having at least one of a structural unit derived from an olefin and a structural unit derived from a conjugated diene, and a structural unit derived from styrene, and the polyisocyanate component (C1) has two or more isocyanates. Isocyanate group-containing compound
Polyamide resin (P2) is
The following (i) and / or (ii), further, the polyamide resin (P2) of (i) satisfies (iii) and (vi), and the polyamide resin (P2) of (ii) is (iv). Satisfying ~ (vi),
Compound (C2) satisfies the following (vii).
The polyurethane resin (P3) is a polyurethane polyurea resin.
The polyimide resin (P4) contains a structural unit derived from an aromatic carboxylic acid polyanhydride and a structural unit derived from a polyamine compound having a hydrocarbon group having 20 to 60 carbon atoms, and the hydrocarbon group having 20 to 60 carbon atoms. More than 70% by mass of the group is derived from the hydrocarbon skeleton.
The reactive functional groups are amine and / and acid anhydride groups.
The thermosetting resin composition for a heat conductive material according to [1], wherein the bifunctional or higher functional compound (C4) is an epoxy compound.
(I) The polyamide resin (P2) is a polyamide (A) containing the phenolic hydroxyl group and a hydrocarbon group having 20 to 60 carbon atoms (however, the aromatic ring to which the phenolic hydroxyl group is bonded is not included) in the same polymer. -1).
(Ii) The polyamide resin (P2) is a polyamide (A-1) in which a polyamide (a-1) containing a phenolic hydroxyl group as a side group and a polyamide (a-2) containing a hydrocarbon group having 20 to 60 carbon atoms are mixed. -3).
(Iii) As the monomer constituting the polyamide (A-1), a monomer having a phenolic hydroxyl group and a monomer having a hydrocarbon group having 20 to 60 carbon atoms are included.
(Iv) The polybasic acid monomer and / and the polyamine monomer constituting the polyamide (a-1) contain a monomer having a phenolic hydroxyl group, and the polybasic acid monomer and the polyamine The monomer does not contain a monomer having a hydrocarbon group having 20 to 60 carbon atoms.
(V) The polybasic acid monomer and / and the polyamine monomer constituting the polyamide (a-2) contain a monomer having a hydrocarbon group having 20 to 60 carbon atoms, and the polyamine is added. The basic acid monomer and the polyamine monomer do not contain a monomer having a phenolic hydroxyl group.
(Vi) At least a part of the monomer having a hydrocarbon group having 20 to 60 carbon atoms contains a compound having a cyclic structure having 5 to 10 carbon atoms.
The (vii) compound (C2) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, a carbodiimide group-containing compound, a metal chelate, a metal alkoxide, and a metal acylate.
[3]: As the thermal conductive filler, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, beryllium, aluminum oxide, aluminum nitride, boron nitride. The thermal curing for heat conductive materials according to [1] or [2], which is at least one selected from the group consisting of fused silica, crystalline silica, non-crystalline silica, silicon carbide, silicon nitride, titanium carbide, and diamond. Sex resin composition.
[4]: The thermosetting resin for a heat conductive material according to any one of [1] to [3], which is any of powder, film, sheet, plate, pellet, paste and liquid. Composition.
[5]: A cured product of the thermosetting resin composition for a heat conductive material, which is obtained by curing the thermosetting resin composition for a heat conductive material according to any one of [1] to [4] by heating.
[6]: An electronic component comprising a cured product of the thermosetting resin composition for a heat conductive material according to [5].
[7]: The electronic component according to [6], wherein the cured product is a circuit board or an insulating layer formed on the circuit board.
[8]: The electronic component according to [6], wherein the cured product is used as an adhesive or a sealing material.
[9]: An electronic device equipped with the electronic component according to any one of [6] to [8].

According to the present invention, it is possible to provide a highly reliable thermosetting thermosetting resin composition having excellent thermal conductivity and dielectric properties, a cured product thereof, an electronic component, and an electronic device.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the numerical value specified in this specification is a value obtained by the method disclosed in Embodiment or Example. Further, the numerical values "A to B" specified in the present specification refer to a range satisfying a value larger than the numerical value A and the numerical value A and a value smaller than the numerical value B and the numerical value B. Further, the sheet in the present specification includes not only a sheet defined in JIS but also a film. Unless otherwise specified, the various components mentioned in the present specification may be used independently or in combination of two or more.

The thermosetting resin composition for a heat conductive material of the present embodiment (hereinafter, also referred to as “thermosetting resin composition”) includes any of the following binder components (I) to binder components (IV) and heat conduction. Contains a sex filler. The binder component (I) contains a styrene-based elastomer (P1) having an anhydride group of a carboxylic acid and a polyisocyanate component (C1) that reacts with the anhydride group. The binder component (II) contains a polyamide resin (P2) having a phenolic hydroxyl group as a side group and a trifunctional or higher functional compound (C2) capable of reacting with the phenolic hydroxyl group. The binder component (III) contains a polyurethane resin (P3) having a carboxyl group and an epoxy compound (C3) capable of reacting with the carboxyl group. The binder component (IV) is a polyimide resin (P4) having a reactive functional group and containing a hydrocarbon group having 20 to 60 carbon atoms, and a bifunctional or higher functional compound (C4) that reacts with the reactive functional group. contains. Further, the relative permittivity of the cured product after curing the thermosetting resin composition of the present embodiment is 4.0 or less at a frequency of 5 GHz and 23 ° C., and the dielectric loss tangent is 0.010 or less at a frequency of 5 GHz and 23 ° C. To do.

Since the thermosetting resin composition of the present embodiment has excellent thermal conductivity, it is suitably used for applications that require thermal conductivity, particularly applications that require heat dissipation. Since the thermosetting resin composition of the present embodiment is melted by heating and then cured to exhibit adhesiveness, it can be used as an adhesive material. Further, by utilizing the moldability of the resin composition, it can be suitably used as a heat radiating component having a desired shape. In particular, it is useful as a heat radiating member for electronic devices (smartphones, doublet terminals, etc.) and battery exterior materials in which fans and heat sinks cannot be installed due to lightness, thinness, and miniaturization.

Further, since the thermosetting resin composition of the present embodiment is excellent in dielectric properties in addition to thermal conductivity, the insulating layer forming material on the circuit board itself or the circuit board (coverlay layer of printed wiring board, built-up substrate). (Including interlayer insulating layer, substrate forming material, bonding sheet, etc.), resin casting material such as underfill material, sealing material for semiconductor chips, material for forming the insulating layer of semiconductor chip packages, etc. Used. It is also suitable as a bonding material between components such as an electronic circuit board and an electronic component. A bonding sheet can be exemplified as a suitable example of this bonding material. Since the binder component of the present embodiment has excellent electrical insulating properties, a cured product having excellent insulating properties can be provided by using a thermosetting resin composition that satisfies the relative permittivity and the dielectric loss tangent of the present embodiment.

The thermosetting resin composition can be in the form of powder, film, sheet, plate, pellet, paste or liquid, for example. The liquid or paste-like thermosetting resin composition can be easily obtained by adjusting the viscosity with a solvent. Further, the film-shaped, sheet-shaped, and plate-shaped thermosetting resin compositions can be formed, for example, by applying a liquid or paste-shaped thermosetting resin composition and drying it. Further, the powdery or pelletized thermosetting resin composition can be obtained, for example, by pulverizing or dividing the film-like thermosetting resin composition into a desired size.

At the stage of the thermosetting resin composition, the thermosetting resin may be partially reacted with the curing agent, or may be semi-cured (B-staged). The cured product of the thermosetting resin composition of the present embodiment is obtained by curing the thermosetting resin composition by heating. It may be pressurized at the time of heating.

As described above, the relative permittivity of the cured product after curing the thermosetting resin composition of the present embodiment is 4.0 or less at a frequency of 5 GHz and 23 ° C., and the dielectric loss tangent is 0. It shall be 010 or less. More preferably, the relative permittivity is 3.5 or less and the dielectric loss tangent is 0.005 or less, and even more preferably, the relative permittivity is 3.2 or less and the dielectric loss tangent is 0.003 or less. The lower limit of the relative permittivity and the dielectric loss tangent is not particularly limited, but usually the relative permittivity is 2.0 or more and the dielectric loss tangent is 0.001 or more. The relative permittivity and dielectric loss tangent of the cured product of the thermosetting resin composition can be adjusted by adjusting the type of resin, the type and amount of filler of the thermosetting resin composition.

The cured product of the thermosetting resin composition of the present embodiment is excellent in electrical insulation, thermal conductivity, and dielectric properties by using the binder components (I) to (IV) and the thermally conductive filler in combination. It can be suitably applied to an insulating member of a component. Examples of electronic components include semiconductor devices and circuit boards.

The semiconductor device is, for example, a power module such as a power semiconductor device, an LED, an inverter device, and the semiconductor device includes, for example, an insulated gate bipolar transistor, a diode, a semiconductor element such as an IC chip, and various heat generating elements such as a resistor and a capacitor. Is installed. The cured product of the thermosetting resin composition of the present embodiment is used for a substrate, an insulating layer, a sealing material, an insulating layer of a semiconductor chip package, an underfill material, an adhesive, and the like of a semiconductor device.

Examples of the circuit board include a printed wiring board, a metal layer not classified as a printed wiring board, a laminated body for a circuit board composed of a laminated body including an insulating resin layer, and the like. The cured product of the thermosetting resin composition of the present embodiment is, for example, as an insulating layer which is a constituent layer of a laminated substrate, or a bonding sheet with a coverlay layer, a protective layer, other members, parts, etc. of a printed wiring board. It is preferably used as. The cured product of the thermosetting resin composition of the present embodiment may be a cured product of a prepreg. In this case, the base material may be impregnated with the thermosetting resin composition of the present embodiment and the semi-cured prepreg may be finally obtained as a cured product. A known material can be applied to the base material.

Further, the cured product of the thermosetting resin composition of the present embodiment is suitable as an adhesive layer or a heat spreader between a heating element and a heat sink. Further, it can be applied as a heat radiating layer for covering one or a plurality of electronic components mounted on a substrate.

[Glue conductive adhesive]
A conductive filler can be further added to the thermosetting resin composition of the present embodiment to be used as an anisotropic conductive adhesive. An anisotropic conductive adhesive made by adding a conductive filler to a thermosetting resin composition using a binder component and a thermally conductive filler that satisfy the relative permittivity and dielectric properties of the present embodiment has excellent thermal conductivity. It exhibits excellent dielectric properties in the cured portion of the property and thermosetting resin composition. Therefore, by using the anisotropic conductive adhesive of the present embodiment for a component for high frequency applications, it is possible to exhibit better adhesive performance while maintaining good transmission characteristics.

For example, an anisotropic conductive adhesive can be used as a bonding layer of the electromagnetic wave shield layer of the printed wiring board with the electromagnetic wave shield layer. Further, it can be used as an anisotropic conductive connection film (for example, bonding between circuits, chip mounting, bonding between substrates, etc.) as a substitute for solder. According to the anisotropic conductive adhesive of the present embodiment, the dielectric properties of the components of the cured product other than the conductive filler are excellent, so that the heat conductivity and the signal transmission loss in the high frequency band (MHz to GHz band) are lost. Can be effectively suppressed. As described above, the anisotropic conductive adhesive of the present embodiment can provide a material exhibiting anisotropic conductivity having excellent thermal conductivity and dielectric properties.

The anisotropic conductive adhesive can be used, for example, in the form of a film or a sheet. Examples of the conductive filler include metal-based fillers. Examples of the metal filler include metal powders such as silver, copper and nickel, alloy powders such as solder, silver-coated copper powder, gold-coated copper powder, silver-coated nickel powder, and gold-coated nickel powder. By containing silver, more excellent conductivity can be obtained. Of these, silver-coated copper powder is particularly preferable from the viewpoint of cost. The coverage of the coat layer on the metal powder is preferably 80% or more on the surface.

In the conductive filler, the coating layer for coating the nucleolus may cover at least a part of the nucleolus, but in order to obtain better conductive properties, a higher coverage is preferable. From the viewpoint of maintaining good conductive properties, the average coverage of the coating layer is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

<< Thermal Conductive Filler >>
The thermally conductive filler used in the present embodiment is a compound that imparts thermal conductivity to the cured product of the thermosetting resin composition for a thermally conductive material of the present embodiment. From the viewpoint of thermal conductivity, the thermally conductive filler preferably has a thermal conductivity of 10 W / m · K or more, more preferably 15 W / m · K or more, and 20 W / m · K or more. Is even more preferable. As the heat conductive filler, a heat conductive inorganic filler and a heat conductive organic-inorganic hybrid filler can be used.

Specific examples of the heat conductive inorganic filler include alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, beryllia, aluminum oxide, aluminum nitride, and nitride. Metal oxides and metal nitrides such as boron; hydrated metal compounds; silica-based materials such as molten silica, crystalline silica, and non-crystalline silica; nitride-based and carbon-based fillers such as silicon carbide, silicon nitride, titanium carbide, and diamond. Can be exemplified.

Among these, alumina, aluminum oxide, aluminum nitride and boron nitride are more preferable, and alumina and boron nitride are particularly preferable from the viewpoint of heat resistance, thermal conductivity and low dielectric constant. The combined use of alumina and boron nitride is also suitable. When alumina and boron nitride are used in combination, the mass ratio of boron nitride / alumina is preferably in the range of 60/40 to 95/5, more preferably 80/20 to 95/5. By setting the boron nitride / alumina in the range of 60/40 to 95/5, there is an effect that the adhesiveness is more excellent while being excellent in heat resistance, low dielectric constant and thermal conductivity. The thermally conductive filler is used alone or in combination of two or more.

Specific examples of the thermally conductive organic-inorganic hybrid filler include fillers in which the surface of the above-mentioned inorganic filler is coated with a resin or a dispersant. As a method of coating the surface of the thermally conductive inorganic filler with a resin or a dispersant, a known method can be applied. In this case, it is preferable that the inorganic filler is exposed in order to effectively bring out the thermal conductivity characteristics of the thermally conductive inorganic filler. The surface of the thermally conductive inorganic filler can be surface-treated with, for example, a silane-based, titanate-based, or aluminate-based coupling agent. By the surface treatment, the dispersibility of the thermally conductive filler attached to the binder component can be enhanced. In addition, the interfacial adhesive strength between the binder component and the thermally conductive filler can be increased.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, and γ-aminopropyltri. Aminosilanes such as methoxysilane and γ-ureidopropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Epoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; p-styryltrimethoxysilane, vinyltricrolsilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyl Examples thereof include vinyl silane such as trimethoxysilane.

Examples of the titanate coupling agent include isopropyltriisostearoyl titanate, isopropyltri (N-aminoethyl / aminoethyl) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, and bis ( Examples thereof include dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, diisopropylbis (dioctylphosphate) titanate, tetraisopropylbis (dioctylphosphate) titanate, and tetraoctylbis (ditridecylphosphate) titanate.

Further, it is also preferable to coat the surface of the thermally conductive inorganic filler with a fluororesin. From the viewpoint of maintaining good thermal conductivity, it is preferable that the thermally conductive inorganic filler is exposed at the portion where the thermally conductive inorganic fillers come into contact with each other.

From the viewpoint of more effectively reducing the dielectric constant, it is also preferable to use a fluorine-based filler in combination with the thermally conductive inorganic filler. Fluorine-based fillers include PTFE, PVDF (vinylidene fluoride polymer having a linear structure in which CF ₂ and CH ₂ are alternately bonded), and neobron FEP (tetrafluoroethylene to hexafluoropropylene copolymer: tetrafluoride). Ethylene to propylene hexafluoropolymer copolymer resin), PFA (tetrafluoroethylene to perfluoroalkyl vinyl ether copolymer: perfluoroalkoxy resin), neophron ETFE (tetrafluoroethylene and ethylene copolymer), ECTFE (polychlorotri) Fluoroethylene: tetrafluoroethylene chloride resin) and the like can be exemplified. Among these, a combination of a polytetrafluoroethylene PTFE filler and a thermally conductive filler, particularly a thermally conductive inorganic filler, is preferable.

The fluorine-based filler may contain fillers such as glass fiber, carbon fiber, graphite, bronze, molybdenum disulfide, and carbon.

The suitable range of the average particle size (D50) calculated by the laser diffraction / scattering method of the thermally conductive filler may vary depending on the application, but can be, for example, 0.1 to 250 μm. Nano-order particles and micro-order particles may be used in combination. Further, the particle shape can be exemplified by a spherical shape, a needle shape, a flake shape, a dendritic shape, a fibrous shape, or the like. By using a plurality of types of thermally conductive fillers having different particle sizes and shapes, it may be possible to highly fill the thermally conductive filler.

The content of the thermally conductive filler in the thermosetting resin composition can be appropriately adjusted depending on the application. From the viewpoint of the balance between thermal conductivity and adhesive properties and flexibility, it is preferable to set the thermal conductive filler in the range of 30 to 500 parts by mass with respect to 100 parts by mass of the thermosetting resin.

<< Binder component >>
Hereinafter, preferred embodiments of the binder component (I) to the binder component (IV) will be described.

[[Binder component (I)]]
The binder component (I) is a styrene-based elastomer (P1) having an carboxylic acid anhydride group (hereinafter, may be abbreviated as an acid anhydride group) and a polyisocyanate component (C1) that reacts with the acid anhydride group. Contains. In the present specification, the "elastomer" refers to a polymer having rubber elasticity at room temperature without being vulcanized. In terms of chemical structure, those having an ABA type block or (AB) n type multi-block structure are generally used. Further, the styrene-based elastomer refers to a copolymer having a block having polystyrene (hereinafter, also referred to as a polystyrene block).

<Styrene-based elastomer (P1)>
It is important that the styrene-based elastomer (P1) has an anhydride group of a carboxylic acid. By reacting the acid anhydride group in the styrene-based elastomer (P1) with the polyisocyanate component (C1) described later, it is possible to form an imide group having excellent heat resistance and a function of suppressing the dielectric constant and dielectric loss tangent. .. A preferred example of the styrene-based elastomer (P1) is a block copolymer having at least one of a structural unit derived from an olefin and a structural unit derived from a conjugated diene, and a structural unit derived from styrene. Excellent heat resistance can be realized by using a styrene-based elastomer (P1) having a polystyrene structure in the molecule. Specific examples include styrene-butadiene block copolymer, styrene-ethylene-propylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and styrene-ethylene-butylene-styrene. Examples thereof include block copolymers, styrene-ethylene-propylene block copolymers, styrene-isoprene-styrene block copolymers and the like. In these styrene-based elastomers (P1), the parts other than the polystyrene block are collectively regarded as one block. Further, among the parts other than the polystyrene block, as a block formed from units (residues) derived from two or more monomers, in the above example, from a copolymer composed of ethylene and propylene, or from ethylene and butylene. Can be exemplified. The block formed from units derived from two or more monomers other than such a polystyrene block may be a random copolymer or a block copolymer.

The imide group can also be formed by the reaction of the acid anhydride group and the amino group, but it is not preferable in the following points. The first-stage reaction between the acid anhydride group and the amino group, that is, the ring-opening reaction of the acid anhydride group by the amino group is extremely fast, so that there is a problem that the pot life as a thermosetting adhesive is shortened. is there. The second-stage reaction between the acid anhydride group and the amino group, that is, the imide group formation reaction by the ring closure of the amic acid, is higher in temperature than the imide group formation reaction by the reaction between the acid anhydride group and the isocyanate group. Requires heating. If the heating is insufficient, the amic acid, which is a precursor of the imide group, remains, and the dielectric constant and the dielectric loss tangent become high. Further, if the amic acid remains, when the thermosetting resin is cured, the imidization reaction accompanied by the elimination of water may explosively proceed and foaming may occur. When the anhydride group and the isocyanate group of the carboxylic acid are heat-cured at about 150 to 200 ° C., the heat resistance and the insulating property are improved, the dielectric constant and the dielectric adjunct are lowered, and the above-mentioned carboxylic acid anhydride is used. As in the case of the reaction between the group and the amino group, a new peak is observed near 1700 cm- ² in the infrared absorption spectrum, so it is considered that the imide group was formed.

The method of introducing an acid anhydride group into a styrene elastomer (P1) is a method of polymerizing a monomer having an acid anhydride group as one of the raw materials for producing a styrene elastomer (P1) with another raw material, a polymer. Examples thereof include a method of introducing an acid anhydride group into the side chain after synthesis and a method of causing a grafting reaction. For example, a method of copolymerizing an anhydride of an ethylenically unsaturated carboxylic acid such as maleic anhydride in an appropriate amount, after synthesizing a styrene-based elastomer (P1), an anhydride of an ethylenically unsaturated carboxylic acid such as maleic anhydride in an appropriate amount. Examples thereof include a method of carrying out a grafting reaction using a substance and a peroxide. Further, instead of the acid anhydride, an appropriate amount of an ethylenically unsaturated carboxylic acid such as maleic acid can be used. In this case, at least a part of the carboxylic acid is made into an anhydride group after introduction.

The styrene-based elastomer (P1) preferably contains 5 to 60% by mass of polystyrene blocks, more preferably 10 to 50% by mass, still more preferably, in 100% by mass excluding the anhydride of the ethylenically unsaturated carboxylic acid. Is 20-40% by mass. When the polystyrene block is 5% by mass or more, a cured product having excellent viscoelasticity can be obtained, and when the polystyrene block is 60% by mass or less, the solubility in a solvent is improved, and the thermosetting resin composition Excellent solution stability.

Acid anhydride group value of the styrene-based elastomer (P1) is preferably 0.1~40mgCH ₃ ONa / g, more preferably 1~30mgCH ₃ ONa / g, more preferably 5~20mgCH ₃ ONa / g Is. By using a styrene-based elastomer (P1) having an acid anhydride base value of 0.1 mgCH ₃ ONa / g or more, the adhesiveness can be improved, and the heat resistance and the insulating property are improved. By using a styrene-based elastomer (P1) having an acid anhydride base value of 40 mgCH ₃ ONa / g or less, a low dielectric constant required for a printed wiring board or the like to which a high-frequency electric signal propagates can be exhibited.

A styrene-based elastomer (P1) in which a part of the acid anhydride group is ring-opened with water, alcohol, amine, or the like and is in the state of carboxylic acid can also be used as the styrene-based elastomer (P1). Since a part of the acid anhydride group is opened to form a carboxylic acid, it can be expected that the adhesive strength to the conductive circuit described later will be improved. However, if all of the acid anhydride groups are ring-opened to form a carboxylic acid, the reaction with the polyisocyanate component (C1) described later produces an amide group instead of an imide group, which is a dielectric positive contact. Becomes larger.

The ratio of the acid anhydride to the ring-opened carboxylic acid is preferably acid anhydride: carboxylic acid = 100 to 50: 0 to 50 in molar ratio, more preferably 100 to 75: 0 to 25. , More preferably 100 to 85: 0 to 15. The ratio of the acid anhydride group to the ring-opened carboxylic acid can be determined by the following method. That is, the amount (mg) of sodium methoxide required to neutralize 1 g of the styrene-based elastomer (P1) is determined, and this is taken as the total acid value. By dividing the total acid value by the molecular weight of sodium methoxide, the amount of carboxylic acid contained in 1 g of the styrene elastomer (P1): X (mmol) is determined. The total acid value includes both a carboxylic acid in which the acid anhydride group contained in 1 g of the styrene elastomer (P1) is ring-opened at the time of acid value measurement and a carboxylic acid that has already been ring-opened at the time of acid value measurement. .. Separately, the amount of perchloric acid (mmol) required to neutralize 1 g of the styrene-based elastomer (P1) was determined as the acid anhydride base value, and this was converted into the amount of sodium methoxide (mg) to obtain acid anhydride. Use as the base price. By dividing the acid anhydride base value by the molecular weight of sodium methoxide, the amount of the acid anhydride group contained in 1 g of the styrene elastomer (P1): Y (mmol) can be determined.
When 1 mol of the acid anhydride group opens a ring, it becomes 2 mol of a carboxylic acid. Therefore, the amount of the carboxylic acid contained in 1 g of the styrene-based elastomer (P1) and already opened at the time of acid value measurement is Z (mmol). Then
Z = X-2Y.
That is, the ratio of the acid anhydride contained in the styrene elastomer (P1) to the ring-opened carboxylic acid is
Y: Z = Y: (X-2Y).
The molecular weight of sodium methoxide, which is the standard of total acid value, and the molecular weight of potassium hydroxide, which is the standard of acid anhydride base value, are close to each other. Therefore, assuming that the total acid value is X', the acid anhydride base value is Y', and the acid value derived from the carboxylic acid that has already been ring-opened at the time of acid value measurement is Z'.
Simply
Z'= X'-2Y'can be set,
The ratio of the acid anhydride contained in the styrene elastomer (P1) to the ring-opened carboxylic acid is
Y': Z'= Y': (X'-2Y').

The styrene-based elastomer (P1) preferably has a mass average average molecular weight of about 5,000 to 1,000,000, more preferably 10,000 to 500,000, and 25,000 to 200,000. Is more preferable, and those of 25,000 to 100,000 are more preferable.

Examples of commercially available styrene-based elastomers (P1) include Tough Tech M series manufactured by Asahi Kasei Corporation and Kraton FG series manufactured by Kraton Polymer Japan. It is used alone or in combination of two or more.

<Polyisocyanate component (C1)>
By the reaction of the polyisocyanate component (C1) with the above-mentioned styrene-based elastomer (P1), a cured product having excellent heat resistance and insulating properties and low dielectric constant and dielectric loss tangent can be obtained. The polyisocyanate component (C1) is preferably an isocyanate group-containing compound having two or more isocyanates. Further, adhesiveness can be imparted. The isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule.

Specific examples of the isocyanate group-containing compound having two isocyanate groups in one molecule include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, and 4,4'-diphenylmethane. Aromatic diisocyanates such as diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene Aliper diisocyanates such as diisocyanates,
ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate , 1,3-Tetramethylxylylene diisocyanate and other aromatic aliphatic diisocyanates,
3-Isocyanate Methyl-3,5,5-trimethylcyclohexylisocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexane Diisocyanates, methyl-2,6-cyclohexanediisocyanates, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane and other alicyclic diisocyanates Can be mentioned.

Specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aromatic polyisocyanates such as 2,4,6-triisocyanate toluene and 1,3,5-triisocyanatebenzene. Examples thereof include aliphatic polyisocyanates such as lysine triisocyanate, aromatic aliphatic polyisocyanates such as 4,4', 4 "-triphenylmethane triisocyanate, alicyclic polyisocyanates, and the diisocyanate trimethylolpropane described above. Examples include an adduct body, a burette body that has reacted with water, and a trimer having an isocyanurate ring.

A blocked isocyanate in which at least a part of the isocyanate group of the polyisocyanate component (C1) is blocked by a blocking agent may be used. Specific examples thereof include those in which the isocyanate group of the polyisocyanate component (C1) is blocked with ε-caprolactam, MEK (methylethylketone) oxime, cyclohexanone oxime, pyrazole, phenol and the like. In particular, the use of a hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is highly preferable because it enhances the adhesive strength to polyimide or copper and has excellent heat resistance.

The content of the isocyanate group of the polyisocyanate component (C1) with respect to 1 mol of the acid anhydride group in the styrene elastomer (P1) is preferably in the range of 0.1 to 20 mol, more preferably in the range of 0.5 to 10 mol, and 1 The range of ~ 3 mol is more preferable. By setting the content of the isocyanate group to 0.1 mol or more with respect to the acid anhydride group in the styrene elastomer (P1), the crosslink density can be increased and the heat resistance, insulating property, and adhesiveness can be improved. By setting the content of the isocyanate group to 20 mol or less, the formation of new polar groups can be suppressed and the decrease in dielectric loss tangent can be suppressed.

<Silane coupling agent, thiol compound>
The thermosetting resin composition using the binder component (I) may contain a silane coupling agent and / or a thiol compound as long as the physical properties are not impaired. By reacting a silane coupling agent or / and a thiol compound with, for example, a styrene-based elastomer (P1), a cured product having excellent heat resistance and insulating properties and low dielectric constant and dielectric loss tangent can be obtained. Further, adhesiveness can be imparted. Further, by using a silane coupling agent and a thiol compound, the adhesiveness to a conductive pattern represented by copper, a conductive layer and a resin film can be improved. Further, the dielectric constant and the dielectric loss tangent are not deteriorated, and the solder heat resistance after humidification, the flexibility of the cured product of the thermosetting resin composition, and the electrical insulation property can be improved.

Examples of the silane coupling agent include a silane coupling agent having N, S or O and / or a hydrolyzed condensate thereof. For example, vinylmethoxysilane, vinylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N -2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane Hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-isocyanuppropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 1,2-ethanediamine, N- { 3- (Trimethoxysilyl) propyl}-, N-{(ethenylphenyl) methyl} derivative / hydrochloride, vinyltriacetoxysilane, allyltrimethoxysilane, and silane coupling in which functional groups are protected by alkoxy groups Agents, sulfide / polysulfide-based silane coupling agents, polymer-type alkoxy oligomer-type agents, polyfunctional group-type silane coupling agents, and the like can be used.

The thiol compound contains, for example, a thiol group and at least a linear or branched chain hydrocarbon group or a cyclic hydrocarbon group. It may contain two or more thiol groups. The hydrocarbon group may be saturated or unsaturated. A part of the hydrogen atom of the hydrocarbon group may be substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, an alkoxysilyl group or the like. As an example of colorless thiols, 1-propanethiol, 3-mercaptopropionic acid, (3-mercaptopropyl) trimethoxysilane, 1-butanethiol, 2-butanethiol, isobutylmercaptan, isoamylmercaptan, cyclopentanethiol, 1 -Hexanethiol, cyclohexanethiol, 6-hydroxy-1-hexanethiol, 6-amino-1-hexanethiol hydrochloride, 1-heptanethiol, 7-carboxy-1-heptanethiol, 7-amide-1-heptanethiol, 1-octane thiol, tert-octane thiol, 8-hydroxy-1-octane thiol, 8-amino-1-octane thiol hydrochloride, 1H, 1H, 2H, 2H-perfluoro octane thiol, 1-nonan thiol, 1- Decanthiol, 10-carboxy-1-decanethiol, 10-amide-1-decanethiol, 1-naphthalenethiol, 2-naphthalenethiol, 1-undecanethiol, 11-amino-1-undecanethiol hydrochloride, 11-hydroxy -1-Undecane thiol, 1-dodecane thiol, 1-tetradecane thiol, 1-hexadecane thiol, 16-hydroxy-1-hexadecane thiol, 16-amino-1-hexadecane thiol hydrochloride, 1-octadecan thiol, 1,4- Butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,2-benzenedithiol, 1,9-nonandithiol, 1,10-decandithiol, 1,3,5-benzenetrithiol, 3- Examples thereof include mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Thiols can be used alone or in combination of two or more.

The amount of the silane coupling agent or / and the thiol compound contained in the thermosetting resin composition containing the binder component (I) is not particularly limited, but is based on 100 parts by mass of the solid content of the styrene elastomer (P1). The total content is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 25 parts by mass, and even more preferably 1 to 15 parts by mass. By containing a thiol compound and a silane coupling agent (which does not contain sulfur atoms), in addition to improving dimensional stability and heat resistance after humidification as a cured product when curing a thermosetting resin composition. It is possible to improve the performance, which is easily contradictory to both adhesiveness and low dielectric constant, and electrical insulation, in a more balanced manner.

The thermosetting resin composition containing the binder component (I) can further contain a filler for the purpose of imparting flame retardancy and the like. For example, in addition to polytetrafluoroethylene powder, polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., a multilayer using silicone, acrylic, styrene butadiene rubber, butadiene rubber, etc. Polymer fillers such as structural core shells;
(Poly) phosphate systems such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate, etc. Phosphates such as compounds, organic phosphate compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphite, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, etc. Phosphate-based flame-retardant fillers such as acid compounds, phosphine oxide compounds, phosphorane compounds, and phosphoramide compounds;
Nitrogen-based flame-retardant fillers such as benzoguanamine, melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole compound, tetrazole compound, diazo compound, urea, etc.;
Silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonotrite, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate, sepiolite, magnesium sulfate, zinc hydroxide, barium hydroxide. , Calcium hydroxide, titanium oxide, tin oxide, zirconium oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, barium carbonate, zinc borate, aluminum borate and other inorganic fillers.

Considering the environmental impact that has been discussed in recent years, it is desirable to use a non-halogen flame retardant such as a phosphorus-based flame retardant or a nitrogen-based flame retardant. Among them, phosphazene compounds, phosphine compounds, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, hydroxide compounds and the like can be exemplified as fillers that are more effective in flame retardancy when used in combination with the binder component (I). Further, in terms of further reducing the dielectric constant and the dielectric loss tangent, the use of polytetrafluoroethylene powder and phosphine compound is preferable, and the balance between adhesiveness, flexibility, electrical insulation and heat resistance is excellent as well as dielectric properties. It becomes possible to obtain a cured product. The filler may be used alone or in combination of two or more.

The total content of the entire filler can be, for example, 0.01 to 500 parts by mass with respect to 100 parts by mass of the styrene elastomer (P1). The filler can improve the modifying effect and the mechanical properties of the cured product.

As a method for adding a filler (including a thermally conductive filler), a conventionally known method can be used without limitation. For example, there is a method in which a dispersion containing a filler is prepared and the dispersion containing the filler is kneaded with a reaction solution containing a filler before, during, or after the polymerization of the styrene elastomer (P1) by a three-roll or the like. Further, in order to disperse the filler well and stabilize the dispersed state, a dispersant and / or a thickener may be used within a range that does not affect the characteristics.

<Other ingredients>
In addition to the essential component and the above-mentioned optional component, the binder component (I) further includes an epoxy group-containing compound, an oxetane group-containing compound, an aziridine group-containing compound, a carbodiimide group-containing compound, and a benzoxazine compound as long as the purpose is not impaired. , Β-Hydroxyalkylamide group-containing compounds can be added. In addition, dyes, pigments, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion collectors, moisturizers, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, UV absorbers. , Infrared absorbers and the like can be included.

Examples of the epoxy group-containing compound include epoxy resins such as glycisyl ether type epoxy resin, glycisyl amine type epoxy resin, glycidyl ester type epoxy resin, and cyclic aliphatic (alicyclic) epoxy resin. Examples of the glycidyl ether type epoxy resin include cresol novolac type epoxy resin, phenol novolac type epoxy resin, α-naphthol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, tetrabrombisphenol A type epoxy resin, and brominated phenol novolac. Examples thereof include type epoxy resins, tris (glycidyloxyphenyl) methane, and tetrakis (glycidyloxyphenyl) ethane. Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, tetraglycidylmethoxylylenediamine and the like. Although examples of the oxetane group-containing compound, the aziridine compound, the carbodiimide group-containing compound, the benzoxazine compound, and the β-hydroxyalkylamide group-containing compound are omitted, known compounds can be appropriately selected and used.

[[Binder component (II)]]
The binder component (II) is a polyamide resin (P2) containing a phenolic hydroxyl group in the side group (hereinafter, also referred to as “polyamide resin (P2)”) and a trifunctional or higher functional compound capable of reacting with the above-mentioned phenolic hydroxyl group. (C2) (hereinafter, also referred to as “compound (C2)”) is contained.

<Polyamide resin (P2)>
The polyamide resin (P2) is a polybasic acid compound usually selected from a divalent or higher polybasic acid and / or acid anhydride and / or a lower alkyl ester thereof as a monomer, and a divalent or higher polyamine compound. Is synthesized using and. The phenolic hydroxyl group in the polyamide resin (P2) can form a crosslinked structure by thermosetting with a trifunctional or higher functional compound (C2).
Preferable examples of the polyamide resin (P2) include the following (i) and / or (ii). That is, the polyamide (P2) of (i) is a polyamide containing a phenolic hydroxyl group and a hydrocarbon group having 20 to 60 carbon atoms (however, the aromatic ring to which the phenolic hydroxyl group is bonded is not included) in the same polymer. A-1). The polyamide (P2) of (ii) does not contain a polyamide (a-1) containing a phenolic hydroxyl group as a side group and a hydrocarbon group having 20 to 60 carbon atoms (however, the aromatic ring to which the phenolic hydroxyl group is bonded). ) Is a mixed polyamide (A-3) with the polyamide (a-2).

The former polyamide (A-1) is preferable from the viewpoint of solubility in a general-purpose solvent and productivity. In the following description, the parentheses of the hydrocarbon group having 20 to 60 carbon atoms (however, the aromatic ring to which the phenolic hydroxyl group is bonded are not included) are omitted, but "the hydrocarbon group having 20 to 60 carbon atoms" is omitted. , The condition of the parentheses is satisfied. Further, "hydrocarbon group having 20 to 60 carbon atoms" is also referred to as "C20 to 60 hydrocarbon group". The hydrocarbon group having 20 to 60 carbon atoms refers to a hydrocarbon group having 20 to 60 carbon atoms contained in all or a part of residues other than the functional group that contributes to the polymerization of the monomer. Count the number of carbon atoms in a continuous structure that does not contain elements other than hydrogen. More preferably, all the residues other than the functional group that contributes to the polymerization of the monomer are hydrocarbon groups having 20 to 60 carbon atoms. That is, it refers to the total number of carbons of a main chain and a side group or a continuous hydrocarbon group directly connected to the main chain with respect to the obtained polyamide (A-1), and is an aliphatic (including an alicyclic type). ), Aromatic rings are also counted. However, it is assumed that the aromatic ring to which the phenolic hydroxyl group is bonded is not included. Further, the hydrocarbon groups bonded via the aromatic ring to which the phenolic hydroxyl groups are bonded are counted as separate hydrocarbon groups.

Further, as a preferable example of the polyamide resin (P2) of (i), a polyamide resin satisfying the following (iii) and (vi), and as a preferred example of the polyamide resin (P2) of (ii), (iv) to (vi) A polyamide resin satisfying the above can be mentioned.
(Iii) As the monomer constituting the polyamide (A-1), a monomer having a phenolic hydroxyl group and a monomer having a hydrocarbon group having 20 to 60 carbon atoms are included. Needless to say, a monomer having a phenolic hydroxyl group and a hydrocarbon group having 20 to 60 carbon atoms may be used in the same type of monomer.
(Iv) The polybasic acid monomer and / and the polyamine monomer constituting the polyamide (a-1) contain a monomer having a phenolic hydroxyl group, and the polybasic acid monomer and the polyamine single amount. The body does not contain a monomer having a hydrocarbon group having 20 to 60 carbon atoms.
(V) The polybasic acid monomer or / and the polyamine monomer constituting the polyamide (a-2) contains a monomer having a hydrocarbon group having 20 to 60 carbon atoms, and is a monobasic acid monomer. The metric and polyamine monomer do not contain a monomer having a phenolic hydroxyl group.
(Vi) A monomer having a hydrocarbon group having 20 to 60 carbon atoms contains a compound having a cyclic structure having 5 to 10 carbon atoms. In addition, "containing a compound having a cyclic structure having 5 to 10 carbon atoms" means that at least a part of a monomer having a hydrocarbon group having 20 to 60 carbon atoms has a cyclic structure having 5 to 10 carbon atoms. It means that a monomer comprising the above is contained.

The monomer having a hydrocarbon group having 20 to 60 carbon atoms is more preferably a monomer having a hydrocarbon group having 24 to 56 carbon atoms from the viewpoint of effectively drawing out solubility and flexibility. A monomer having a hydrocarbon group of 28 to 48 is more preferable, and a monomer having a hydrocarbon group of 36 to 44 carbon is further preferable.

By using the polyamide resin (P2), it is possible to provide a cured product of a thermosetting resin composition having excellent moisture heat resistance and flexibility without impairing heat resistance and chemical resistance. Further, there is an advantage that a thermosetting resin composition that can be used for a wide range of versatile organic solvents can be provided. In addition, by using the binder component (II) and the thermally conductive filler, it has excellent electrical insulation and thermal conductivity, and the dielectric constant and dielectric loss tangent of high-frequency circuits such as printed wiring boards on which high-frequency electrical signals propagate. Can be significantly improved. Also, when folding a circuit board (metal-clad laminate, printed wiring board, etc.) containing a cured product of a heat-curable resin composition, heat resistance during solder reflow, and adhesiveness to metals such as copper and polyimide substrates. Flexibility is obtained.

A monomer having a phenolic hydroxyl group is used as a monomer constituting the polyamide resin (P2), and a functional group (phenolic hydroxyl group) serving as a cross-linking point is introduced into a side group of the main chain skeleton to thermoset. It is possible to increase the cross-linking density and impart heat resistance during solder reflow. The phenolic hydroxyl group of the side group is a polybasic acid compound having a phenolic hydroxyl group (polybasic acid monomer) or / and a polyamine compound having a phenolic hydroxyl group (polyamine) as a raw material of the polyamide resin (P2) as described later. (Polymer) can be used. Further, by introducing a C20 to 60 hydrocarbon group into the polyamide resin (P2), the concentration of the amide bond having a high water absorption rate can be relatively lowered, so that the insulation reliability and the dielectric property can be improved. Further, the flexibility can be improved by the flexibility peculiar to the C20 to 60 hydrocarbon groups and by introducing a phenolic hydroxyl group into the monomer constituting the polyamide resin (P2). Therefore, the thermosetting resin composition containing the binder component (II) can be suitably used as an insulating layer such as a coverlay layer of a printed wiring board or the like, which is required to have foldability and the like.

By containing a compound having a cyclic structure having 5 to 10 carbon atoms as a monomer having a C20 to 60 hydrocarbon group in the polyamide resin (P2), the molecular arrangement is inhibited and the crystallinity is lowered. Can be done. As a result, the solubility can be improved. Further, a compound having a cyclic structure having 5 to 10 carbon atoms is more effective because it has a structure containing a hydrocarbon group such as a chain-like alkyl group having a high degree of freedom and hydrophobicity in a portion other than the cyclic structure. It has the effect of effectively increasing the solubility and effectively lowering the dielectric constant and the dielectric loss tangent. The C20-60 hydrocarbon group is introduced by using a polybasic acid compound having a C20-60 hydrocarbon group and / or a polyamine compound having a C20-60 hydrocarbon group as a raw material of the polyamide resin (P2) as described later. it can.

Since the polyamide resin (P2) has two structures of a phenolic hydroxyl group and a C20 to 60 hydrocarbon group, it can be dissolved in a general-purpose organic solvent, and therefore has excellent thermal conductivity when used in combination with a thermally conductive filler. At the same time, the dielectric constant and the dielectric loss tangent can be lowered, and the two conflicts of both adhesiveness and heat resistance and both flexibility and electrical insulation can be solved. Hereinafter, preferred forms of the polyamides (A-1) and (A-3) will be described in detail.

<Polyamide (A-1)>
Polyamide (A-1) is formed by polymerizing a polybasic acid monomer (m ₁ ) and a polyamine monomer (m ₂ ), has a phenolic hydroxyl group as a side group, and is contained in the same polymer. It has a phenolic hydroxyl group and a C20-60 hydrocarbon group. That is, the polybasic acid monomer (m ₁ ) is at least selected from the group consisting of a polybasic acid compound having a phenolic hydroxyl group, a polybasic acid compound containing a C20-60 hydrocarbon group, and other polybasic acid compounds. From one, the polyamine monomer (m ₂ ) is a phenol in the polymer from at least one selected from the group consisting of polyamine compounds having phenolic hydroxyl groups, polyamine compounds containing C20-60 hydrocarbon groups, and other polyamine compounds. It may be selected so as to contain a sex hydroxyl group and a C20-60 hydrocarbon group. Compounds containing C20-60 hydrocarbon groups and compounds having phenolic hydroxyl groups are monobasic acid monomers (m ₁ ) and polyamines so that they are contained within the same type of monomer or in another monomer. Polyamine (A-1) can be obtained by selecting a monomer (m ₂ ) and polymerizing it.

Here, "to be contained in the same type of monomer" means a polybasic acid compound having a phenolic hydroxyl group as a polybasic acid monomer (m ₁ ) and a polybasic acid containing a C20-60 hydrocarbon group. It means that a compound may be used, or a polyamine compound having a phenolic hydroxyl group as a polyamine monomer (m ₂ ) and a polyamine compound containing a C20 to 60 hydrocarbon group may be used. Further, "to be contained in another monomer" means that the polybasic acid compound (m ₁ ) contains a polybasic acid compound having a phenolic hydroxyl group, and the polyamine monomer (m ₂ ) is C20. It may contain a polyamine compound containing ~ 60 hydrocarbon groups, or may contain a polyamine compound containing C20-60 hydrocarbon groups as a polybasic acid monomer (m ₁ ), and may contain a polyamine monomer (m _2). ) May include a polyamine compound having a phenolic hydroxyl group. In any case, other polybasic acid compounds and other polyamine compounds can be appropriately used.

The phenolic hydroxyl group introduced into the side group of the main chain generated by the polymerization of the polybasic acid monomer (m ₁ ) and the polyamine monomer (m ₂ ) functions as a cross-linking point. That is, a dense crosslinked structure can be formed by thermosetting the polyamide (A-1) and the trifunctional or higher functional compound (C2) that can react with the phenolic hydroxyl group described later. As a result, the heat resistance at the time of soldering after thermosetting is also improved.

Further, the C20 to 60 hydrocarbon groups have a function of lowering the concentration of the highly hygroscopic amide bond and imparting / improving flexibility and flexibility. As a result, the hygroscopicity of the cured product after thermosetting is lowered, the moist heat resistance is improved, and low dielectric constant and low dielectric loss tangent, which are important factors in a printed wiring board through which high-frequency electric signals are propagated, can be achieved. ..

The polybasic acid compound as a polybasic acid monomer (m ₁ ) and the polyamine compound as a polyamine monomer (m ₂ ) may be a divalent or higher-valent monomer, and a trivalent or higher-valent monomer is also appropriate. Used. An appropriate molecular weight may be adjusted by combining a divalent monomer and a trivalent or higher valent monomer to introduce a branched structure. It is also possible to use a monovalent monomer to maintain an appropriate molecular weight. By including a monomer having a valence of 3 or more in a part, the effect that the cohesive force can be increased can be obtained. The amount of the trivalent or higher-valent monomer is preferably 0.1 to 20 mol% in all the monomers, and more preferably 1 to 10 mol% or less.

一般式（１）中、Ｒ_１は、構造単位毎に独立の構造を有していてもよい多塩基酸化合物残基である２価の連結基であり、Ｒ_２は、構造単位毎に独立の構造を有していてもよいポリアミン化合物残基である２価の連結基であり、Ｒ_１およびＲ_２の少なくとも一方は、フェノール性水酸基を有する連結基を含み、且つＲ_１およびＲ_２の少なくとも一方は、Ｃ２０〜６０炭化水素基を有する連結基を含む。ポリアミド（Ａ−１）は、−ＣＯ−Ｒ_１−ＣＯ−ＮＨ−Ｒ_２−ＮＨ−で示される構造単位が少なくとも２以上繰り返されたものである。なお、本実施形態の趣旨を逸脱しない範囲において、一般式（１）の構造単位を１つ有し、且つ末端が封止された化合物が熱硬化性樹脂組成物に含まれてもよい。 When a polyamide resin (P2) is obtained by using a dibasic acid monomer and a diamine monomer, it has a structural unit of the following general formula (1).

In the general formula (1), R ₁ is a divalent linking group which is a polybasic acid compound residue which may have an independent structure for each structural unit, and R ₂ is independent for each structural unit. structure is a divalent linking group is a good polyamine compound residue which may have a, at least one of R ₁ and R ₂ includes a linking group having a phenolic hydroxyl group, and R ₁ and R ₂ At least one comprises a linking group having a C20-60 hydrocarbon group. Polyamide (A-1) is obtained by repeating at least two or more structural units represented by -CO-R _1- CO-NH-R _2- NH-. The thermosetting resin composition may contain a compound having one structural unit of the general formula (1) and having a sealed end, as long as the gist of the present embodiment is not deviated.

The phenolic hydroxyl group-containing monomer and the C20 to 60 hydrocarbon group-containing monomer need only be contained in at least one of the dibasic acid compound and the diamine compound, and the dibasic acid compound and the diamine compound may be contained. Both of these groups may be contained in each of the above. For example, when two dibasic acid compounds R _1-1 and R _1-2 and two diamine compounds R _2-1 and R _2-2 are used, -CO-R _1-1- CO-NH-R _{2 -1-} NH-, -CO-R _1-1- CO-NH-R _2-2 -NH-, -CO-R _1-2- CO-NH-R _2-1 -NH-, -CO-R _1-2- CO-NH-R _2-2- NH- structural units may be included.

<Polybasic acid monomer (m ₁ )>
[Polybasic acid compound with phenolic hydroxyl group]
The polybasic acid compound having a phenolic hydroxyl group is not particularly limited, but hydroxyisophthalic acid such as 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid and 5-hydroxyisophthalic acid, 2,5-dihydroxyisophthalic acid and 2,4- Dihydroxyisophthalic acid, dihydroxyisophthalic acid such as 4,6-dihydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,3-dihydroxyterephthalic acid, dihydroxyterephthalic acid such as 2,6-dihydroxyterephthalic acid, 4-hydroxyphthalic acid, Hydroxyphthalic acid such as 3-hydroxyphthalic acid, dihydroxyphthalic acid such as 3,4-dihydroxyphthalic acid, 3,5-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid and 3,6-dihydroxyphthalic acid can be mentioned. Be done. Further, these acid anhydrides and ester derivatives such as polybasic acid methyl ester can also be mentioned. The only difference is that in the case of free polybasic acids and acid anhydrides, there is a dehydration reaction, and in the case of ester derivatives, there is a corresponding dealcoholization reaction. Of these, 5-hydroxyisophthalic acid is preferable from the viewpoint of copolymerizability and easy availability. When 5-hydroxyisophthalic acid is used, R ₁ in the general formula (1), that is, the divalent linking group which is a polybasic acid compound residue, is two carboxyl groups from the 5-hydroxyisophthalic acid. This is the excluded part.

[Polybasic acid compound containing C20-60 hydrocarbon groups]
As a preferred example of the polybasic acid compound containing a C20 to 60 hydrocarbon group, a monobasic unsaturated fatty acid having at least one double bond or triple bond having 10 to 24 carbon atoms was reacted. Examples thereof include a polybasic acid compound having a cyclic structure having 5 to 10 carbon atoms. An example of the reaction is the Diels-Alder reaction. For example, a dimer obtained by a deal-alder reaction using natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, and rapeseed oil fatty acid and purified oleic acid, linoleic acid, linolenic acid, erucic acid, etc. A polybasic acid compound containing a modified fatty acid (dymer acid) is preferably used. The cyclic structure may be one or two, and in the case of two, the two rings may be independent or continuous. Examples of the cyclic structure include a saturated alicyclic structure, an unsaturated alicyclic structure, and an aromatic ring. Although the carboxyl group can be directly bonded to the cyclic structure, it is preferable that the carboxyl group is bonded to the cyclic structure via an aliphatic chain from the viewpoint of improving solubility and flexibility. The number of carbon atoms between the carboxyl group and the cyclic structure is preferably 2 to 25. Further, the polybasic acid compound containing a C20 to 60 hydrocarbon group has a chain shape having a high degree of freedom and hydrophobicity as a portion other than the cyclic structure from the viewpoint of improving solubility, improving flexibility, and lowering dielectric constant and dielectric loss tangent. It is preferable to have an alkyl group of. It is preferable that the number of alkyl groups is two or more for one cyclic structure. The alkyl group preferably has 2 to 25 carbon atoms.

Polybasic acid compounds containing C20-60 hydrocarbon groups usually contain a monomer containing a dimer derived from dimer acid (dimerized fatty acid) as a residue as a main component, and other fatty acids as raw materials and three It is obtained as a composition of fatty acids that is more than dimerized. Among them, the content of the monomer containing a dimer derived from dimer acid (dimerized fatty acid) as a residue is 70% by mass or more in 100% by mass of the monomer containing a C20 to 60 hydrocarbon group. It is preferably 95% by mass or more. Further, a dimer whose degree of unsaturation is lowered by hydrogenation (hydrogenation reaction) is particularly preferably used from the viewpoint of oxidation resistance (particularly coloring in a high temperature range) and suppression of gelation during synthesis. As the polybasic acid compound having a C20 to 60 hydrocarbon group, a monomer (polybasic acid compound) containing a dimer derived from a monobasic unsaturated fatty acid having 10 to 24 carbon atoms as a residue can be used. preferable. Further, as a part of the polybasic acid compound having a C20-60 hydrocarbon group, a monomer containing a trimer, which is a tricarboxylic acid, derived from a monobasic unsaturated fatty acid having 10 to 24 carbon atoms as a residue is used. Is preferable.

The polybasic acid compound having a C20 to 60 hydrocarbon group can be obtained by a known reaction, but a commercially available product can also be used. Examples of commercially available products include "Pripole 1004", "Pripole 1006", "Pripole 1009", "Pripole 1013", "Pripole 1015", "Pripole 1017", "Pripole 1022", and "Pripole 1022" manufactured by Clauder Japan. "1025", "Pripole 1040" and "Empole 1008", "Empole 1012", "Empole 1016", "Empole 1026", "Empole 1028", "Empole 1043", "Empole 1061", "Empole 1061" made by BASF Japan "Empole 1062" and the like. These polybasic acid compounds can be used alone or in combination. Among them, "Pripole 1009" having 36 carbon atoms can be preferably used from the viewpoint that a polyamide having excellent heat resistance, moisture heat resistance and dielectric constant can be obtained while maintaining adhesiveness. Further, since the prepole 1004 has a structure having 44 carbon atoms, it can be suitably used from the viewpoint that a polyamide having excellent dielectric constant and flexibility can be obtained. Further, when "Pripol 1040" containing about 75% by mass of a tricarboxylic acid component which is a trimer is used, the cohesive force of the polyamide can be improved, and it can be suitably used from the viewpoint of improving heat resistance.
The cohesive force can also be improved by using a trifunctional or higher functional monomer exemplified as one of the "other polybasic acid compounds" described later as a trifunctional polybasic acid compound. However, while the trifunctional or higher molecular weight monomer described later has a relatively low molecular weight, the tricarboxylic acid component, which is the trimer described above, has a relatively large molecular weight, so that the concentration of the amide bond can be efficiently reduced. , Dielectric coefficient and dielectric loss tangent can be reduced, which is more preferable.

[Other polybasic acid compounds]
The polybasic acid compound other than the polybasic acid compound having a phenolic hydroxyl group and the polybasic acid compound having a C20-60 hydrocarbon group is not particularly limited as long as it does not deviate from the gist of the present embodiment, but is a dibasic acid compound. And trifunctional or higher functional polybasic acid compounds can be mentioned.
Examples of the dibasic acid compound include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. Aromatic dibasic acids such as: oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, apple acid, tartaric acid, thioapple acid, pimeric acid, suberic acid, azelaic acid , Sebacic acid, dodecanedioic acid, hexadecandioic acid, diglycolic acid and other aliphatic dibasic acids; 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid and other fats Examples include cyclic dibasic acid. Examples of the trifunctional or higher functional polybasic acid compound include trimellitic acid, hydrogenated trimellitic acid, pyromellitic acid, hydrogenated pyromellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like.

These polybasic acid compounds may be used alone or in combination with respect to the polybasic acid compound having a phenolic hydroxyl group or the polybasic acid compound having a C20-60 hydrocarbon group. Good. Among them, isophthalic acid and 1,4-cyclohexanedicarboxylic acid can be preferably used from the viewpoint that a tough polyamide having more excellent heat resistance can be obtained while maintaining flexibility. Further, by using a trifunctional or higher functional material, a branched structure can be introduced into the polyamide to increase the molecular weight, and the cohesive force of the obtained polyamide can be increased. As a result, dimensional stability and heat resistance can be particularly improved without adversely affecting adhesiveness, flexibility, and electrical insulation.

Further, a monofunctional basic compound can be used in combination with the polybasic acid compound. By using a monofunctional compound, the carboxyl group and amino group that can be the terminal functional group of the polyamide can be reduced, and the molecular weight of the obtained polyamide can be controlled. As a result, the stability of the polyamide resin over time can be improved. Examples of the monobasic acid compound include benzoic acid, 4-hydroxybenzoic acid, 2-ethylhexanoic acid and the like.

<Polyamine monomer (m ₂ )>
The polyamine compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include polyamines represented by the following general formula (2).

In the formula, R ₃ represents a group consisting of a direct bond or carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, for example, a part of hydrogen by a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen atom. Alternatively, all substituted divalent hydrocarbon groups having 1 to 30 carbon atoms,-(C = O)-, -SO _2- , -O-, -S-, -NH- (C = O)- ,-(C = O) -O-, a group represented by the following general formula (3) and a group represented by the following general formula (4). In the formula, r and s each independently represent an integer of 1 to 20, and R ₄ represents a hydrogen atom or a methyl group.

The above R ₃ is preferably directly bonded.

When the compound of the general formula (2) is used, R ₂ in the general formula (1), that is, the divalent linking group which is a polyamine compound residue is two amino groups from the compound of the general formula (2). It is the part excluding.

[Polyamine compound containing C20-60 hydrocarbon groups]
Examples of the polyamine compound containing a C20 to 60 hydrocarbon group include the above-mentioned compound obtained by converting a carbocyclyl group of a polybasic acid compound having a C20 to 60 hydrocarbon group into an amino group, and examples of commercially available products include clogder. Examples thereof include "Priamine 1071", "Priamine 1073", "Priamine 1074" and "Priamine 1075" manufactured by Japan, and "Versamine 551" manufactured by BASF Japan. These polyamine compounds can be used alone or in combination. Among them, "Priamine 1071" containing about 20 to 25% by mass of a triamine triamine component can improve the cohesive force of the polyamide and can be suitably used from the viewpoint of improving heat resistance. Further, the use of triamine, which is a trimer, is preferable in terms of the effect of lowering the dielectric constant and the dielectric loss tangent. From the viewpoint of the production stability of the polyamide, the trimer triamine and the tricarboxylic acid described above total 0.1 to 20 mass by mass in 100% by mass of all the monomers used for forming the polyamide. It is preferably%, and more preferably 1 to 10% by mass.

[Other polyamine compounds]
Next, the polyamine compound other than the polyamine compound having a phenolic hydroxyl group and the polyamine compound having a C20 to 60 hydrocarbon group is not particularly limited as long as it does not deviate from the gist of the present embodiment, but a diamine compound, a triamine compound and the like can be used. Can be mentioned. Examples of the diamine compound include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, and 2,6. -Diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1 , 2-Diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,3 Aromatic diamines such as'-diaminodiphenylsulfone; ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12 -Adiamine polyamines such as dodecamethylenediamine and metaxylene diamine; isophoronediamine, norbornandiamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, Examples include alicyclic diamines such as piperazine. Examples of the trifunctional or higher functional polyamine compound include 1,2,4-triaminobenzene, 3,4,4'-triaminodiphenyl ether, and the like. If the amino group is not directly connected even if it has an aromatic ring, it is classified as an aliphatic or the like.

These polyamine compounds may be used alone or in combination with respect to the polyamine having a phenolic hydroxyl group or the polyamine having a C20-60 hydrocarbon group. Among them, isophorone diamine and norbornane diamine can be preferably used from the viewpoint that a tough polyamide having more excellent heat resistance can be obtained while maintaining flexibility.

Further, by using a trifunctional or higher functional material, a branched structure can be introduced into the polyamide to increase the molecular weight, and the cohesive force of the obtained polyamide can be increased. As a result, dimensional stability and heat resistance can be particularly improved without adversely affecting adhesiveness, flexibility, and electrical insulation.

Furthermore, monofunctional amine compounds can also be used in combination with polyamine compounds. By using a monofunctional compound, the carboxyl group and amino group that can be the terminal functional group of the polyamide can be reduced, and the molecular weight of the obtained polyamide can be controlled. As a result, the stability of the polyamide resin over time can be improved. On the other hand, if the carboxyl group or amino group that can be the terminal functional group is not reduced by the monofunctional compound, the phenol group, the carboxyl group and / or the amino group will be mixed in the resin, and the phenolic hydroxyl group can be reacted. When a trifunctional or higher functional compound (C2) is used in combination, it is desirable because the processability and adhesiveness can be improved by utilizing the difference in the reactivity of each. Examples of the monofunctional amine compound include aniline, 4-aminophenol, 2-ethylhexylamine and the like.

Polyamide (A-1) contains the above-mentioned polybasic acid monomer (m ₁ ) and polyamine alone, depending on the performance to be particularly improved, such as dimensional stability, adhesiveness, heat resistance, flexibility, and electrical insulation. It can be obtained by appropriately selecting a monomer (m ₂ ).

The polyamide (A-1) obtained by polymerization may be obtained by randomly polymerizing a component having a phenolic hydroxyl group and a component having a C20 to 60 hydrocarbon group, or may be a block polymer. There may be. That is, a mixture of a plurality of types of polybasic acid monomer compounds may be polymerized with a type of polyamine compound, or a mixture of a plurality of types of polybasic acid compounds and a mixture of a plurality of types of polyamine compounds may be polymerized. However, a mixture of one type of polybasic acid compound and a plurality of types of polyamine compounds may be polymerized, or after the polymerization of one type of polybasic acid compound and one type of polyamine compound, depending on the functional group remaining at the terminal, Further, other polybasic acid compounds and other polyamine compounds may be polymerized.

The polyamide (A-1) is a total monomer used, that is, a polybasic acid monomer (m ₁ ), a polyamine monomer (m ₂ ), and a monobasic acid or monofunctional acid used as needed. A compound containing a C20 to 60 hydrocarbon group is preferably contained in an amount of 10 to 95 mol%, more preferably 14 to 92 mol%, and further preferably 18 to 88 mol% in a total of 100 mol of the amine compounds.

A method for calculating the number of moles of a monomer containing a C20-60 hydrocarbon group will be described. First, the molecular weight (M) of the monomer containing a C20 to 60 hydrocarbon group is calculated by the following formula.
M = (56.11 x F x 1000) / E
F: Number of functional groups of the monomer containing C20-60 hydrocarbon groups E: Acid value of the monomer containing C20-60 hydrocarbon groups (mgKOH / g)
Next, the mass of the compound containing the C20 to 60 hydrocarbon groups subjected to the polymerization is divided by the molecular weight (M) to determine the number of moles of the compound containing the C20 to 60 hydrocarbon groups subjected to the polymerization.
In the same manner, the number of moles of each monomer subjected to polymerization is determined, and they are totaled to determine the number of moles of all the monomers subjected to polymerization. Then, by dividing the number of moles of the compound containing C20 to 60 hydrocarbon groups by the number of moles of all the monomers, the proportion (mol%) of the compound containing C20 to 60 hydrocarbon groups can be determined.

≪Polyamide (A-3) ≫
The polyamide (A-3) is a polyamide obtained by mixing polyamide (a-1) and (a-2). Polyamide (a-1) is formed by polymerizing a polybasic acid monomer (m ₃ ) and a polyamine monomer (m ₄ ), has a phenolic hydroxyl group as a side group, and has a C20 to 60 hydrocarbon. It does not have a hydrogen group. Any other polybasic acid monomer or polyamine monomer can be appropriately used as long as the above conditions are satisfied. That is, the polybasic acid monomer (m ₃ ) is composed of a polybasic acid compound having a phenolic hydroxyl group and other polybasic acid compounds (excluding polybasic acid compounds containing C20 to 60 hydrocarbon groups). From at least one selected from the group, the polyamine monomer (m ₄ ) is from the group consisting of polyamine compounds having phenolic hydroxyl groups and other polyamine compounds (excluding polyamine compounds containing C20-60 hydrocarbon groups). From at least one selected, it may be selected so that the polymer contains a phenolic hydroxyl group. At least one of the polybasic acid monomer (m ₃ ) or the polyamine monomer (m ₄ ) has a phenolic hydroxyl group. An appropriate molecular weight may be adjusted by combining a divalent monomer and a trivalent or higher valent monomer to introduce a branched structure. It is also possible to use a monovalent monomer to maintain an appropriate molecular weight. That is, the polyamide (a-1) is a polyamide having a phenolic hydroxyl group as a side group but not a C20 to 60 hydrocarbon group.

On the other hand, the polybasic acid monomer (m ₅ ) is composed of a polybasic acid compound containing a C20-60 hydrocarbon group and other polybasic acid compounds (excluding polybasic acid compounds having a phenolic hydroxyl group). At least one selected from the group, the polyamine monomer (m ₆ ) is a group consisting of a polyamine compound containing a C20-60 hydrocarbon group and other polyamine compounds (excluding polyamine compounds having a phenolic hydroxyl group). At least one of the polybasic acid monomer (m ₅ ) or the polyamine monomer (m ₆ ) is at least one selected from the above, and contains a C20-60 hydrocarbon group. That is, the polyamide (a-2) is a polyamide having a C20-60 hydrocarbon group but not having a phenolic hydroxyl group as a side group.

That is, polyamide (A-3) has a polyamide (a-1) having a phenolic hydroxyl group as a side group but not a C20 to 60 hydrocarbon group, and a polyamide (a-1) having a C20 to 60 hydrocarbon group but having a side group. It is a mixture with polyamide (a-2) which does not have a phenolic hydroxyl group. The trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group, which will be described later, can react with the phenolic hydroxyl group and often reacts with at least one of a carboxyl group and an amino group. When a thermoplastic resin composition containing a polyamide (A-3) and a trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group is thermally cured, a trifunctional or higher functional compound (C2) capable of reacting with the phenolic hydroxyl group ( When C2) that can react with at least one of a carboxyl group and an amino group is used, it has a polyamide (a-1) containing a phenolic hydroxyl group in the polyamide (A-3) and a C20-60 hydrocarbon group. The terminal carboxyl group and terminal amino group of the polyamide (a-2) can also be utilized in the thermal curing reaction.

The mixing ratio of the polyamide (a-1) containing a phenolic hydroxyl group and the polyamide (a-2) having a C20-60 hydrocarbon group shall be appropriately adjusted according to the phenolic hydroxyl group value and molecular weight of (a-1). However, a polyamide containing a phenolic hydroxyl group: a polyamide having a C20 to 60 hydrocarbon group = 5:95 to 80:20 (mass ratio) is preferable, and the ratio is 10:90 to 50:50. Is preferable.

The "mixture" and "mixture" of the polyamide (A-3) mean to include the following cases. That is, when a mixture of the polyamide (a-1) and the polyamide (a-2) is obtained in advance, and then a trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group described later is blended, or the polyamide When (a-1), the polyamide (a-2) and a trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group described later are blended, or the polyamide (a-1) and a phenolic compound described later are blended. It is intended to include the case where the above-mentioned polyamide (a-2) is blended after blending the trifunctional or higher functional compound (C2) capable of reacting with the hydroxyl group, and vice versa.

Examples of the polybasic acid monomer (m ₃ ) include those other than the polybasic acid compound containing a C20 to 60 hydrocarbon group among the polybasic acid monomers (m ₁ ). In addition, monobasic compounds can also be used in combination. Examples of the polyamine monomer (m ₄ ) include polyamine monomers (m ₂ ) other than polyamine compounds containing C20 to 60 hydrocarbon groups. In addition, a monofunctional amine compound can also be used in combination.

Examples of the polybasic acid monomer (m ₅ ) include those other than the polybasic acid compound having a phenolic hydroxyl group among the polybasic acid monomers (m ₁ ). In addition, monobasic compounds can also be used in combination. Examples of the polyamine monomer (m ₆ ) include polyamine monomers (m ₂ ) other than polyamine compounds having a phenolic hydroxyl group. In addition, a monofunctional amine compound can also be used in combination.

The polyamide (A-3) is a total monomer used for formation, that is, a polybasic acid monomer (m ₃ ), a polyamine monomer (m ₄ ), a polybasic acid monomer (m ₅ ), and the like. It is preferable that 10 to 95 mol% of the compound containing a C20 to 60 hydrocarbon group is contained in 100 mol of the total of the polyamine monomer (m ₆ ) and the monobasic acid or monofunctional amine compound used as needed. It is more preferably contained in an amount of ~ 92 mol%, and further preferably contained in an amount of 18 to 88 mol%.

<Specifications of polyamide resin (P2)>
Next, the specifications (phenolic hydroxyl value, weight average molecular weight, glass transition temperature) of the polyamide resin (P2) will be described.

The polyamide resin (P2) may have a carboxyl group or an amino group at the end, or may not have a functional group at the end, as long as the side group of the polyamide contains a phenolic hydroxyl group. The amount of the phenolic hydroxyl group contained in the side group of the polyamide can be appropriately adjusted depending on the type and amount of the trifunctional or higher functional compound (C2) capable of reacting with the phenolic hydroxyl group.

[Phenolic hydroxyl value]
Specifically, the phenolic hydroxyl value of the polyamide resin (P2) is preferably 1 to 80 mgKOH / g, more preferably 5 to 60 mgKOH / g, and even more preferably 5 to 30 mgKOH / g. By using a polyamide having a phenolic hydroxyl value of 1 mgKOH / g or more, a dense crosslinked structure can be formed, and the resistance of the coating film after curing of the thermosetting resin composition can be improved. Further, by using a polyamide having a phenolic hydroxyl value of 80 mgKOH / g or less, a cured coating film having good hardness, adhesiveness and flexibility of a cured product of a thermosetting resin composition can be obtained. Further, when a polyamide having a phenolic hydroxyl value in the range of 1 to 80 mgKOH / g and a range close to 1 mgKOH / g is used, the adhesiveness and flexibility of the obtained coating film are improved, while it is close to 80 mgKOH / g. When a polyamide in the range is used, the number of cross-linking points increases, so that the heat resistance of the finally obtained coating film is improved. As described above, the phenolic hydroxyl value of the polyamide resin (P2) can be adjusted in the range of 1 to 80 mgKOH / g according to the purpose.

In the case of (i), the phenolic hydroxyl group value can be adjusted by the charging ratio (polymerization composition) of the monomer having a phenolic hydroxyl group among the monomers. Further, in the case of (ii), it can be adjusted by the ratio of the monomer having a phenolic hydroxyl group among all the monomers of the polyamides (a-1) and (a-2). For example, if the reaction is carried out using only 5-hydroxyisophthalic acid having a phenolic hydroxyl group as the polybasic acid compound and only dimerdiamine having no phenolic hydroxyl group as the polyamine compound, a polyamide resin (P2) finally obtained can be obtained. ), The phenolic hydroxyl value can be made close to 80 mgKOH / g, and the heat resistance of the cured coating film can be further improved.

In the case of the polyamide (A-3) among the polyamide resins (P2), the phenolic hydroxyl value of the mixture is defined as the phenolic hydroxyl value of the polyamide resin (P2).

[Weight average molecular weight]
Among the polyamide resins (P2), the weight average molecular weight of the polyamide (A-1) is 3,000 to 1,000,000 in terms of handleability, adhesiveness when made into a thermosetting resin composition, and heat resistance. It is preferably 5,000 to 550,000, more preferably 10,000 to 300,000. Among the polyamide resins (P2), the weight average molecular weight of the polyamide (a-1) is preferably 500 to 30,000, preferably 1000 to 20,000, from the viewpoint of solubility in a general-purpose solvent described later. More preferably, it is more preferably 1,000 to 10,000. Further, among the polyamide resins (P2), the weight average molecular weight of the polyamide (a-2) is preferably in the same range as that of the polyamide (A-1).

[Glass transition temperature of polyamide resin (P2)]
The glass transition temperature of the polyamide resin (P2) is preferably −40 ° C. to 120 ° C., more preferably −30 ° C. to 80 ° C. By adjusting the glass transition temperature of the polyamide resin (P2) to the range of -40 ° C to 120 ° C, it is possible to suppress protrusion during hot pressing, and further, good embedding property in the substrate becomes possible, and adhesion is possible. The sex can be further improved.

The glass transition temperature can be adjusted by appropriately setting the ratio of the polybasic acid compound having a C20 to 60 hydrocarbon group or the polyamine compound having a C20 to 60 hydrocarbon group. For example, by increasing the blending ratio of a polybasic acid compound having a C20-60 hydrocarbon group or a polyamine compound having a C20-60 hydrocarbon group, the concentration of an amide bond having a high water absorption rate can be lowered, or a dimerized fatty acid can be obtained. Since the unique flexible flexibility can be imparted, the glass transition temperature can be adjusted in a range close to −40 ° C.

In the case of the polyamide (A-3) among the polyamide resins (P2), the glass transition temperature of the mixture is defined as the glass transition temperature of the polyamide resin (P2).

[Polyamide resin (P2) soluble in organic solvent]
The polyamide resin (P2) is widely soluble in a versatile organic solvent. Soluble means that 5 parts by mass or more is dissolved at 25 ° C. in 95 parts by mass of a mixed solvent of a general-purpose solvent such as a hydrocarbon solvent, an alcohol solvent, a ketone solvent and an ester solvent. Say. In particular, it is preferable to dissolve 5 parts by mass or more at 25 ° C. in 95 parts by mass of a mixed solvent of toluene / isopropanol = 50/50 (mass ratio). Examples of the hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, cyclohexane, hexane and the like. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.

<Synthesis of polyamide resin (P2)>
Subsequently, a method for synthesizing the polyamide resin (P2) will be described. The polymerization conditions of the polyamide resin (P2) are not particularly limited, and melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and known conditions in which these methods are combined can be used. Generally, industrially, the reaction is carried out at 150 to 300 ° C. for about 1 to 24 hours in the presence or absence of a catalyst. In order to promote the dehydration or dealcohol reaction and avoid coloring and decomposition reaction due to high temperature, it is preferable to carry out the reaction at 180 to 270 ° C. under a reduced pressure of atmospheric pressure or less.

When synthesizing a polyamide (A-1) containing a phenolic hydroxyl group, for example, a polybasic acid compound having a phenolic hydroxyl group and / or a polyamine compound having a phenolic hydroxyl group, C20-60 carbonized in a nitrogen-filled flask. A predetermined amount of a polybasic acid compound having a hydrogen group and / or a polyamine compound having a C20 to 60 hydrocarbon group and ion-exchanged water is charged, and the mixture is uniformly dissolved or dispersed by heating and stirring at 20 to 100 ° C. Then, the temperature is gradually raised to 230 ° C. while removing the ion-exchanged water and the water generated by the reaction, and when the temperature reaches 230 ° C., the pressure is reduced to about 15 mmHg and the temperature is maintained for about 1 hour to obtain the polyamide (A-1). be able to. When the polybasic acid compound and the polyamine compound are mixed, a salt is formed and easily solidified. Since the salt formed by mixing the two in the presence of ion-exchanged water dissolves or disperses in the ion-exchanged water, it is preferable to use the ion-exchanged water from the viewpoint of safety and the like.

Specific examples of catalysts that can be used in obtaining polyamide (A-1) include, for example, phosphorous acid, phosphorous acid, hypophosphoric acid, pyrophosphoric acid, polyphosphoric acid, alkali metal salts thereof, and alkaline earth metals. Inorganic phosphorus compounds such as salts, phosphite esters such as triphenyl phosphite and diphenyl phosphite, titanium catalysts such as tetrabutyl orthotitanate and tetraisopropyl orthotitanate, dibutyltin oxide, dibutyltin laurate, monobutyl Examples thereof include tin-based catalysts such as hydroxytin oxide, and zirconium-based catalysts such as tetrabutoxyzaldehyde, zirconium acetate, and zirconium octylate.

These can also be used as a mixture of two or more types. Further, even if these catalysts are contained in the polyamide resin (P2), there is no problem in carrying out the present invention.

The by-product is a catalyst for inorganic salts such as decomposition products of the catalyst used, oxides of decomposition products or modified products thereof, and by-products such as amide compounds such as oligomers, but is contained in the polyamide resin (P2). It does not matter if it is done.

<Trifunctional or higher functional compound (C2) that can react with phenolic hydroxyl groups>
The thermosetting resin composition of the present embodiment contains the above-mentioned polyamide resin (P2) and a trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group. A trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group will be described. As the binder component (II), the compound (C2) is used as the curing agent for the above-mentioned polyamide resin (P2). In addition to the trifunctional or higher functional compound (C2), the bifunctional compound (C) that can react with the phenolic hydroxyl group [hereinafter, also referred to as “compound (C)”] does not deviate from the purpose of the present embodiment. Can be added with. When the compound (C) is added, it is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, with respect to 100 parts by mass of the compound (C2) from the viewpoint of effectively increasing the crosslink density. ..

[Epoxy group-containing compound]
The trifunctional or higher functional epoxy group-containing compound that can be used as the compound (C2) may be a compound having an epoxy group in the molecule, and is not particularly limited, but is a glycisyl ether type epoxy resin or a glycisyl amine type epoxy. An epoxy resin such as a resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (lipid ring type) epoxy resin can be used. From the viewpoint of compatibility with the polyamide resin (P2), an epoxy compound having a viscosity of 10 to 1000000 mPa · S at 25 ° C. is preferable.

Examples of the glycidyl ether type epoxy resin include cresol novolac type epoxy resin, phenol novolac type epoxy resin, tetrakis (glycidyloxyphenyl) ethane and the like. Examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane and tetraglycidylmethoxylylenediamine. As the epoxy group-containing compound, tetrakis (glycidyloxyphenyl) ethane or tetraglycidyldiaminodiphenylmethane is preferably used from the viewpoint of high adhesiveness and heat resistance.

Examples of the glycidyl ether type epoxy resin as the epoxy group-containing compound that can be used as the compound (C) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and dicyclopentadiene type epoxy resin. Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate and the like.
Examples of the cyclic aliphatic (alicyclic) epoxy resin include 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and the like. As the epoxy group-containing compound, the compound (C2) can be used alone or in combination of two or more, or the compound (C2) can be used in combination with the compound (C).

[Isocyanate compound]
The isocyanate group-containing compound that can be used as the compound (C2) is not particularly limited as long as it is a compound having three or more isocyanate groups in the molecule. The isocyanate group may be blocked by a blocking agent or not, and any isocyanate group may be used, but those blocked by a blocking agent are preferable.

The isocyanate group-containing compound that can be used as the bifunctional compound (C) capable of reacting with the phenolic hydroxyl group is not particularly limited, and is, for example, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-. Examples thereof include aromatic diisocyanates such as tolylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate.

The isocyanate group-containing compound that can be used as a trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group is not particularly limited, but for example, the trimethylolpropane adduct of diisocyanate described above and a biuret that has reacted with water. Examples include the body, a trimer having an isocyanurate ring.

The blocked isocyanate compound is not particularly limited as long as the isocyanate group in the isocyanate group-containing compound is protected by ε-caprolactam, MEK oxime, or the like. Specific examples thereof include those in which the isocyanate group of the isocyanate group-containing compound is blocked with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol and the like. In particular, the hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole has not only storage stability but also adhesion to a bonding material such as polyimide or copper when used in the present embodiment. It is highly preferable because it has excellent strength and solder heat resistance.

[Carbodiimide group-containing compound]
Examples of the carbodiimide group-containing compound that can be used as a trifunctional or higher functional compound (C2) that can react with a phenolic hydroxyl group include a carbodilite series manufactured by Nisshinbo. Among them, Carbodilite V-01, 03, 05, 07, 09 is preferable because it has excellent compatibility with an organic solvent.

[Metal chelate compound]
Examples of the metal chelate compound that can be used as a trifunctional or higher functional compound (C2) capable of reacting with a phenolic hydroxyl group include an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound, and the central metal is iron, cobalt, indium, and the like. It is not particularly limited because various metals such as the above can form a chelate bond. The number of functional groups of the metal chelate here and the metal alkoxide and metal acylate described later is calculated as the valence of the central metal, and the compound (C2) is trifunctional or higher, that is, the valence of the central metal is 3 or higher. Can be used as.

Here, as the aluminum chelate compound used for the binder component (II), typical examples thereof include aluminum acetylacetoneate and aluminum ethylacetacetate.

Typical examples of the titanium chelate compound include titanium acetylacetonate, titanium ethylacetate acetate, titanium octylene glycolate, titanium lactate, titanium triethanolaminate, and polytitanium acetylacetylacetonate. Typical examples of the zirconium chelate compound include zirconium acetylacetonate, zirconium ethylacetylacetonate, and zirconium lactate ammonium salt.

[Metal alkoxide]
Examples of the metal alkoxide compound include an aluminum alkoxide compound, a titanium alkoxide compound, and a zirconium alkoxide compound, but the metal alkoxide compound is not particularly limited because various metals such as iron, cobalt, and indium can form an alkoxide bond. Absent.

Typical examples of the aluminum alkoxide compound include aluminum isopropylate, aluminum butyrate, and aluminum ethylate. In addition, typical examples of the titanium alkoxide compound include isopropyl titanate, normal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary amyl titanate, tertiary butyl titanate, and tetrastearyl titanate. In addition, typical examples of the zirconium alkoxide compound include normal propyl zirconeate and normal butyl zirconeate.

[Metal Achillate]
Examples of the metal acylate compound include an aluminum acylate compound, a titanium acylate compound, and a zirconium acylate compound, but the metal acylate compound is particularly limited because various metals such as iron, cobalt, and indium can form an alkoxide bond. It's not a thing.

The trifunctional or higher functional compound (C2) contains three or more functional groups of the same type in one molecule, and also includes functional groups containing a total of three or more functional groups. For example, a mixture of chelate, alkoxide and acylate in one molecule can also be preferably used.

Only one compound (C2) may be used alone, or a plurality of compounds (C2) may be used in combination. When a plurality of them are used in combination, when a polyamide resin (P2) in which a phenol group and a carboxyl group and / or an amino group are mixed is used, a synergistic effect such as improvement of processability and adhesiveness by utilizing the difference in reactivity of each. Is desirable because it exerts. Among them, "at least one selected from the group consisting of metal chelate, metal alkoxide, and metal acylate" and "trifunctional or higher functional epoxy group-containing compound" have significantly different reactivity and different characteristics of physical properties that can be improved. Therefore, a large synergistic effect can be expected, which is preferable. The amount of the compound (C2) to be used may be determined in consideration of the use of the curable resin composition and the like, and is not particularly limited, but is 0.5 with respect to 100 parts by mass of the polyamide resin (P2). It is preferably added at a ratio of ~ 100 parts by mass, and more preferably at a ratio of 1 to 80 parts by mass. By using the compound (C2), the crosslink density of the curable resin composition can be adjusted to an appropriate value, so that various physical properties of the coating film after curing can be further improved. When the amount of the compound (C2) used is close to 0.5 parts by mass, it is possible to suppress the crosslink density of the coating film after heat curing from becoming too high, and it is possible to exhibit desired flexibility and adhesiveness. .. Further, by suppressing the increase of polar functional groups, a desired dielectric constant, dielectric loss tangent, and moisture heat resistance can be exhibited. Further, when the amount used is close to 100 parts by mass, the crosslink density after heat curing can be further increased, and as a result, the coating film resistance such as electrical insulation of the coating film can be improved.

In the binder component (II), a compound capable of reacting with a carboxyl group or a compound capable of reacting with an amino group can be used in combination with the compound (C2). Examples of the compound capable of reacting with the carboxyl group include an aziridine compound, a β-hydroxyalkylamide group-containing compound, and a dicyandiamide. Examples of the compound capable of reacting with the amino group include maleimide compounds.

In particular, 2,2'-bishydroxymethylbutanoltris [3- (1-aziridinyl) propionate], when used in this embodiment, can suppress protrusion during hot pressing and retains the flexibility of the cured coating film. It is preferably used in the present embodiment because the heat resistance can be improved as it is.

The binder component (II) can contain a compound that directly contributes to the curing reaction as a curing accelerator. Examples of the curing accelerator include phosphine compounds, phosphonium salts, imidazole compounds, tertiary amine compounds and the like.

The binder component (II) requires a polyamide resin (P2) and a compound (C2), and can appropriately contain an organic solvent. Examples of the low boiling point solvent include toluene, cyclohexane, hexane, isopropanol, methyl ethyl ketone, ethyl acetate and the like. Examples of the solvent having a high boiling point include carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. The organic solvent may be used alone or in combination as appropriate. When a solvent is used when producing the polyamide resin (P2), it can be used as the binder component (II) containing the solvent, or after distilling off the solvent at the time of producing the polyamide resin (P2), it is newly added. Another solvent can be added to obtain the liquid binder component (II). The solid content of the binder component (II) is, for example, 5 to 80% by mass.

<Other additives>
The binder component (II) can further contain other components (additives) exemplified in the binder component (I) as optional components as long as the purpose is not impaired. Dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion collectors, moisturizers, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, UV absorption Agents, infrared absorbers, fillers and the like can be added. As the filler for applying the flame retardant or the like, the same filler as the binder component (I) can be preferably used. In particular, the present embodiment is applied to an insulating member (for example, a circuit protective film, a coverlay layer, an interlayer insulating material, etc.) that is in direct contact with a circuit for electronic material applications, and a member (printed wiring board, a support substrate, etc.) that can generate high heat around the circuit. When a cured product of the thermosetting resin composition of No. 1 is used, it is preferable to use a flame retardant in combination.

[[Binder component (III)]]
The binder component (III) contains a polyurethane resin (P3) and an epoxy compound (C3) capable of reacting with the polyurethane resin. This polyurethane resin also includes a polyurethane polyurea resin.

The following can be exemplified as a method for synthesizing the carboxyl group-containing polyurethane resin (P3). For example, it can be produced by reacting a polyol compound, a diisocyanate compound, and a diol compound having a carboxyl group. Further, at the time of synthesizing the polyurethane resin (P3), a diisocyanate compound is excessively blended, a carboxyl group-containing urethane prepolymer having an isocyanate group at the terminal is synthesized, and then a diamine compound is reacted to introduce a urethane urea having a urea group. Resin can also be manufactured.

The polyol compound is a compound having a weight average molecular weight of 500 or more and having two or more hydroxyl groups. For example, poly such as polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer of tetramethylene glycol and neopentyl glycol, or random copolymer. Ether polyols; Polyester polyols which are copolymers of polyhydric alcohols or polyether polyols and polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid; glycols Polycarbonate polyols obtained by the reaction of bisphenol with a carbonate, or the reaction of glycol or bisphenol with phosgene in the presence of an alkali; caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyol, water. Examples thereof include polybutadiene-based polyols such as copolymerized polybutadiene polyols and polyols such as silicone-based polyols. Only one kind of these polyol compounds may be used alone, or two or more kinds thereof may be used in combination.

The diol compound having a carboxyl group is not particularly limited as long as it is a compound having two hydroxyl groups and one or more carboxyl groups in the molecule, and for example, dimethylolbutanoic acid, dimethylolpropionic acid, and these. Derivatives (caprolactone adduct, ethylene oxide adduct, propylene oxide adduct, etc.), 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol and the like can be mentioned. Only one kind of these diol compounds having a carboxyl group may be used alone, or two or more kinds thereof may be used in combination.

Examples of the diisocyanate compound include aromatic diisocyanate, aliphatic diisocyanate, aromatic aliphatic diisocyanate, and alicyclic diisocyanate.

Examples of the aromatic diisocyanate include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-. Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 "-Triphenylmethane triisocyanate and the like can be mentioned.

The aliphatic diisocyanate includes, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2, Examples thereof include 4,4-trimethylhexamethylene diisocyanate.

The aromatic aliphatic diisocyanate is, for example, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1, Examples thereof include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

The alicyclic diisocyanate includes, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and the like. Methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane And so on. Only one type of these diisocyanate compounds may be used alone, or two or more types may be used in combination.

The diamine compound acts as a chain extender, for example, diaminobenzene, diaminotoluene, diaminodimethylbenzene, diaminomethicylene, diaminochlorobenzene, diaminonitrobenzene, diaminoazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, Diaminodimethyldiphenyl ether, methylenedianiline, methylenebis (methylaniline), methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), Methylenebis (diethoxyaniline), methylenebis (dibromoaniline), isopropyridene dianiline, hexafluoroisopropyridene dianiline, diaminobenzophenone, diaminodimethylbenzophenone, diaminoanthraquinone, diaminodiphenylthioether, diaminodimethyldiphenylthioether, diaminodiphenylsulfone, diaminodiphenyl Aromatic polyamines such as sulfoxides and diaminofluorene; ethylene polyamines, propane polyamines, hydroxypropane polyamines, butane polyamines, heptane polyamines, hexane polyamines, diamino diethylamines, diaminodipropylamines, azapentane polyamines, triazaundecan polyamines, nonamethylene Polyamines, undecamethylene polyamines, dodecamethylene polyamines, methylpentamethylene polyamines, aliphatic polyamines such as 2,2,4 (or 2,4,4) -trimethylhexamethylene polyamines and polyamine compounds with 20-48 carbon atoms; bis -(4,4'-Aminocyclohexyl) methane, metaxylylene polyamines, paraxylylene polyamines, isophorone polyamines, norbornan polyamines, cyclopentane polyamines, cyclohexane polyamines, piperazins, homopiperazines and other alicyclic polyamines can be used. it can.

As the polyurethane resin (P3), it is preferable to use a urethane urea resin having a urea group introduced therein. By introducing a urea group, it becomes easy to improve the adhesiveness and flexibility.

<Epoxy compound (C3)>
The trifunctional or higher functional epoxy group-containing compound that can be used as the epoxy compound (C3) may be a compound having an epoxy group in the molecule, and is not particularly limited, but is a glycisyl ether type epoxy resin or glycisyl amine type. An epoxy resin such as an epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (lipid ring type) epoxy resin can be used. As a specific example, a compound similar to the compound (C2) exemplified in the binder component (II) can be exemplified. Further, an epoxy compound having at least one nitrogen atom in the molecule can be exemplified.

By using an epoxy compound having at least one tertiary nitrogen atom in the molecule, it is possible to improve the metal adhesiveness and heat resistance while improving the dielectric constant and the dielectric loss tangent. This is because the high reactivity, which is a property peculiar to an epoxy compound having a tertiary nitrogen atom, can increase the reaction rate under predetermined curing conditions, improve the crosslink density of the cured product, and obtain a high elastic modulus. be able to. As a result, the water absorption rate that affects the dielectric properties can be suppressed. In addition, the nitrogen atom can take various coordination forms, strongly supports the adhesion between the metal and the organic compound, and has excellent metal adhesion.

When an epoxy compound having at least one tertiary nitrogen atom in the molecule is used, the reaction rate under predetermined curing conditions can be increased by the nitrogen atom contained in the compound, so that the unreacted low molecular weight compound It is possible to suppress a decrease in elastic modulus and an increase in water absorption rate due to the above, and further, it is possible to enhance metal adhesion derived from a nitrogen atom, so that good dielectric properties and various properties can be satisfied at the same time. The epoxy compound having at least one tertiary nitrogen atom in the molecule is not particularly limited as long as it has at least one nitrogen compound in the compound containing an epoxy group in the molecule. .. Specific examples of the epoxy compound having at least one tertiary nitrogen atom in the molecule include N-glycidyl phthalimide and epoxy compounds having a structure represented by the following formulas (5) to (15).

However, X represents an aliphatic group or an aromatic group having 0 to 6 carbon atoms, respectively, and Y represents a methylene group, an ethylene group, a trimethylene group, an ethylidene group, an isopropylidene group, a vinylene group, a vinylidene group, an oxy group, It represents any of an imino group, a thio group, and a sulfonyl group, R _{1 to} R ₃ represent a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, and j represents an integer of 0 to 4.

All of them are excellent in terms of dielectric properties from the viewpoint of thermosetting property and low moisture absorption, and are preferable. In particular, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-m-xylene diamine, triglycidyl-m-aminophenol, triglycidyl-p-aminophenol, 4,4'-methylenebis [N, N-bis (oxylanylmethyl) aniline] is polyfunctional When used as the binder component (III), the heat resistance of the cured product of the thermosetting resin composition tends to be improved in addition to the dielectric properties, which is particularly preferable. Further, N, N-diglycidylaniline and N, N-diglycidyl toluidine are bifunctional, and when used as the binder component (III), in addition to the dielectric properties, the flexibility of the cured coating film and the adhesion to polyimide and copper It tends to improve the property, which is preferable.

[[Binder component (IV)]]
The binder component (IV) is a polyimide resin (P4) containing a hydrocarbon group having 20 to 60 carbon atoms (hereinafter, also referred to as a hydrocarbon group having C20 to 60) and a bifunctional resin capable of reacting with the polyimide resin (P4). It contains the above compound (C4). The polyimide resin (P4) is obtained through a step of condensing a polyamine compound and a carboxylic acid polyanhydride, a step of forming an imide group, and the like. Here, the polyamine compound is a substance having two or more amino groups per monomer, and is a primary amine or a secondary amine. Further, the carboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups in the molecule. The polyamine compound is preferably a diamine compound, and the carboxylic acid polyanhydride is preferably a tetracarboxylic dianhydride.

The polyimide resin (P4) may contain a hydrocarbon group of C20 to 60 in any of the monomers. As the monomer having a hydrocarbon group of C20 to 60, a diamine compound is preferable from the viewpoint of easiness of synthesizing the monomer. The diamine compound having a hydrocarbon group of C20 to 60 can be obtained, for example, by converting the carboxyl group of the polybasic acid compound containing the hydrocarbon group of C20 to 60 described in the above-mentioned binder component (II) into an amino group. Be done.

The diamine compound containing a hydrocarbon group of C20 to 60 has 5 to 10 carbon atoms and is obtained by reacting a monobasic unsaturated fatty acid having one or more double or triple bonds having 10 to 24 carbon atoms. Examples thereof include a compound in which a carboxyl group of a polybasic acid compound having a cyclic structure (see binder component (II)) is converted into an amino group. For example, a dimer obtained by a deal-alder reaction using natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, and rapeseed oil fatty acid, and purified oleic acid, linoleic acid, linolenic acid, and erucic acid as raw materials. An example is a compound obtained by converting a carboxyl group of a polybasic acid compound containing a converted fatty acid (dimeric acid) into an amino group. The cyclic structure may be one or two, and in the case of two, the two rings may be independent or continuous. Further, it does not have to have a cyclic structure, and may be a mixture of a cyclic structure and a compound having no cyclic structure. By using the diamine compound derived from the dimer acid, the dimer skeleton can be easily introduced into the polyimide resin (P4).

Examples of the cyclic structure include a saturated alicyclic structure, an unsaturated alicyclic structure, and an aromatic ring. The amino group (amino group converted from the carboxyl group) can be directly bonded to the cyclic structure, but from the viewpoint of improving solubility and flexibility, the amino group is bonded to the cyclic structure via an aliphatic chain. Is preferable. The number of carbon atoms between the amino group and the cyclic structure is preferably 2 to 25. Further, the polyamine compound containing a C20 to 60 hydrocarbon group is a chain alkyl having a high degree of freedom and hydrophobicity as a portion other than the cyclic structure from the viewpoint of improving solubility, improving flexibility, and lowering dielectric constant and dielectric loss tangent. It is preferable to have a group. It is preferable to have two or more alkyl groups for one cyclic structure. The alkyl group preferably has 2 to 25 carbon atoms.

Polyamine compounds containing C20-60 hydrocarbon groups usually contain a monomer containing a dimer skeleton derived from dimer acid (dimerized fatty acid) as a residue as a main component (70% by mass or more), and in addition, It is preferably obtained by converting the carboxyl group of the raw material fatty acid or the composition of the fatty acid of trimerization or more into an amino group. The content of the monomer containing a so-called dimer skeleton, in which the dimer derived from dimer acid (dimerized fatty acid) is a residue, is contained in 100% by mass of the monomer containing a C20-60 hydrocarbon group. 90% by mass or more is more preferable, and 95% by mass or more is further preferable. Further, a dimer whose degree of unsaturation is lowered by hydrogenation (hydrogenation reaction) is particularly preferably used from the viewpoint of oxidation resistance (particularly coloring in a high temperature range) and suppression of gelation during synthesis. As the polyamine compound having a C20 to 60 hydrocarbon group, it is preferable to use a monomer (polyamine compound) containing a dimer derived from a monobasic unsaturated fatty acid having 10 to 24 carbon atoms as a residue. Further, as a part of the polyamine compound having a C20-60 hydrocarbon group, a trimer which is a triamine obtained by converting a tricarboxylic acid derived from a monobasic unsaturated fatty acid having 10 to 24 carbon atoms is used as a residue. It is preferable to use a monomer containing the mixture. By using a polyamine compound having trifunctionality or higher, a branched structure can be introduced into the polyimide resin (P4) to increase the molecular weight, and the cohesive force of the obtained polyimide resin (P4) can be increased.

Commercially available products of dimer diamine include, for example, Priamine 1071, Priamine 1073, Priamine 1074, Priamine 1075 (all manufactured by Croda Japan); Versamine 551 (manufactured by BASF Japan) and the like. Dimer diamine can be used alone or in combination of two or more.

As the polyamine compound used for the polymerization of the polyimide resin (P4), the polyamine compound having a C20 to 60 hydrocarbon group described above may be used exclusively, but other polyamine compounds may be used as long as the gist of the present invention is not deviated. Good. Specific examples include the compounds exemplified in [Other polyamine compounds] described in the binder component (II). The other polyamine compound is preferably 50 mol% or less, more preferably 25 mol% or less, in the total amount of the polyamine compound used for the polyimide resin (P4).

Known monomers can be used as the carboxylic acid polyanhydride. Specifically, pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3, 3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride Anhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic hydride, 4 , 4'-(hexafluoroisopropylidene) diphthalic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-cyclohexene-1,2 dicarboxylic acid anhydride, 1,2,3 , 4-benzenetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic hydride, methylene-4,4'-diphthalic hydride, 1,1-ethylidene-4 , 4'-diphthalic hydride, 2,2-propylidene-4,4'-diphthalic hydride, 1,2-ethylene-4,4'-diphthalic hydride, 1,3-trimethylen- 4,4'-Diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4 '-Oxydiphthalic hydride, p-phenylene bis (trimeritate anhydride), thio-4,4'-diphthalic hydride, sulfonyl-4,4'-diphthalic hydride, 1,3-bis ( 3,4-Dicarboxyphenyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride , 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] Benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-di) Carboxyphenoxy) Dimethylsilane Dianhydride, 1, 3-Bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7 -Anthracenetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride (eg 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2, 3,4-Cyclobutanetetracarboxylic dianhydride, etc.), cyclohexanetetracarboxylic dianhydride (eg, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, etc.), 9,9-bis [4- (3,1-, 3,2-, 3,3- or 3,4-dicarboxyphenoxy) phenyl] Fluorene dianhydride, norbornan-2-spirio-α-cyclopentanone-α'-spirio-2' ′ -Nobornane-5,5'', 6,6''-tetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carcarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,4,5,8-decahydronaphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2, 5,6-Hexahydronaphthalenetetracarboxylic dianhydride, 2,6-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-tetrachloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride , 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-di) Carboxiphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) dianhydride Examples thereof include anhydrides, benzene-1,2,3,4-tetracarboxylic dianhydrides, 3,4,3', 4'-benzophenonetetracarboxylic dianhydrides and the like. Among these, aromatic carboxylic acid polyanhydride is preferable, and aromatic tetracarboxylic dianhydride is more preferable from the viewpoint of adhesiveness and compatibility with amines containing C20 to 60 hydrocarbon groups. Among these, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 from the viewpoint of compatibility with polyamine compounds at the time of synthesis and dielectric properties as a resin. '-Diphenyl ether tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride is particularly preferred. The carboxylic acid polyanhydride may be used alone or in combination of two or more.

More preferred examples of the polyimide resin (P4) include a structural unit derived from an aromatic carboxylic acid polyanhydride and a structural unit derived from a polyamine compound having a hydrocarbon group having 20 to 60 carbon atoms, and have 20 to 60 carbon atoms. Examples thereof include a polyimide resin (P4) in which 70% by mass or more of the hydrocarbon groups are derived from the dimer skeleton.

The reactive functional group of the polyimide resin (P4) is not limited, but at least one of an amino group and an anhydride group is preferable. The reactive functional group is contained in the side chain or the terminal of the polyimide resin (P4). The polyimide resin (P4) having an amine or an anhydride group at the molecular terminal can be easily obtained by adjusting the charge ratio of the diamine compound and the tetracarboxylic dianhydride. More preferably, a polyimide resin (P4) in which an acid dianhydride is excessively blended (blended in an amount of 50 mol% or more) and has an acid anhydride group at the end can be exemplified. In addition, a diamine compound is excessively blended (50 mol% or more is blended) to obtain a polyimide resin having a diamine compound at the terminal or a polyimide resin precursor before forming an imide ring, and then reacted with maleic anhydride. An acid anhydride group may be introduced at the end.

<Synthesis of polyimide resin (P4)>
The polymerization conditions of the polyimide resin (P4) are not particularly limited. For example, it is obtained by polymerizing a polyamine compound and a tetracarboxylic dianhydride in a solvent. Specifically, a polyamic acid solution can be obtained by heating at, for example, 50 to 150 ° C. for about 0.1 to 4 hours in an organic solvent in the presence or absence of a catalyst. Then, for example, a polyimide resin is obtained by dehydration cyclization at 80 to 250 ° C. for 0.5 to 20 hours. The polymerization reaction may be controlled by adding an end sealant. The end sealant is not particularly limited, and known ones can be used. In synthesizing the polyimide resin (P4), known additives such as a dehydrating agent and a reaction catalyst can be appropriately used.

The weight average molecular weight of the polyimide resin (P4) is preferably in the range of 10,000 to 120,000 from the viewpoint of handleability, adhesiveness when made into a thermosetting resin composition, and heat resistance, and is preferably 12,000. It is more preferably 100,000, and even more preferably 15,000 to 70,000.

The acid value of the polyimide resin (P4) is not particularly limited, but is preferably 0.5 to 100, more preferably 1 to 60, and even more preferably 2 to 30. By setting the value to 0.5 to 100, a resin having better adhesiveness and heat resistance can be obtained.

The amine value of the polyimide resin (P4) is not particularly limited, but is preferably 0 to 50, more preferably 0 to 45, and even more preferably 0 to 30. By setting the value from 0 to 50, a resin having excellent pot life can be obtained as a thermosetting resin composition.

<Compound with bifunctionality or higher (C4)>
The bifunctional or higher functional compound (C4) is a compound having a group capable of reacting with a reactive functional group of the polyimide resin (P4) to construct a crosslinked structure. Preferable examples include an epoxy compound having a bifunctional or higher functional epoxy group, an isocyanate compound having a bifunctional or higher isocyanate group, a maleimide compound having a bifunctional or higher maleimide group, and a carbodiimide compound having a bifunctional or higher carbodiimide group. it can. Of these, epoxy compounds are preferable from the viewpoint of producing a cured product having excellent heat resistance and adhesiveness and excellent dielectric properties.

Among the epoxy compounds, a trifunctional or higher functional epoxy compound is preferable from the viewpoint of increasing the crosslink density of the cured product to more effectively enhance the adhesiveness and heat resistance. As the trifunctional or higher functional epoxy compound, an epoxy resin such as a glycisyl ether type epoxy resin, a glycisyl amine type epoxy resin, a glycidyl ester type epoxy resin, or a cyclic aliphatic (alicyclic) epoxy resin can be used. Specific examples include the binder component (II) and the compounds exemplified in the binder component (III). From the viewpoint of improving metal adhesiveness and heat resistance while improving the dielectric constant and dielectric loss tangent, an epoxy compound having at least one nitrogen atom in the molecule is preferable, and an epoxy compound having a tertiary nitrogen atom is preferable. More suitable.

Due to the high reactivity which is a property peculiar to the epoxy compound having a tertiary nitrogen atom, the reaction rate under predetermined curing conditions can be increased, the crosslink density of the cured product can be improved, and a high elastic modulus can be obtained. .. As a result, the water absorption rate that affects the dielectric properties can be suppressed. In addition, the nitrogen atom can take various coordination forms, strongly supports the adhesion between the metal and the organic compound, and has excellent metal adhesion.

When an epoxy compound having at least one tertiary nitrogen atom in the molecule is used, the reaction rate under predetermined curing conditions can be increased by the nitrogen atom contained in the compound, so that the unreacted low molecular weight compound It is possible to suppress a decrease in elastic modulus and an increase in water absorption due to the above. Furthermore, since the metal adhesion derived from the nitrogen atom can be enhanced, good dielectric properties and various properties can be satisfied at the same time. The epoxy compound having at least one tertiary nitrogen atom in the molecule is not particularly limited as long as it has at least one nitrogen compound in the compound containing an epoxy group in the molecule. .. Examples of the epoxy compound having at least one tertiary nitrogen atom in the molecule include epoxy compounds having a structure represented by the formulas (5) to (15) exemplified by the binder component (III).

Examples of the isocyanate compound include the compounds listed in the compound (C2) exemplified in the binder component (II). Further, examples of the carbodiimide group-containing compound include the compounds exemplified in the binder component (II).

According to the thermosetting resin composition in which the binder component (IV) is combined with the heat conductive filler, a highly reliable composition having excellent heat conductivity and dielectric properties can be provided. Preferable examples of the thermally conductive filler are as described above. As a particularly preferable example, a combination of the binder component (IV) and the boron nitride filler and a combination of the binder component (IV) and the boron nitride / alumina are preferable, and the boron nitride / alumina is 60/40 to 95 / by mass ratio. It is more preferable to use it in the range of 5. By using the binder component (IV) and boron nitride / alumina in the range of 60/40 to 95/5, it is possible to provide a cured product having a better balance of adhesive strength, dielectric properties and thermal conductivity.

[[Thermosetting resin composition]]
In addition to the above-mentioned components, an antioxidant can be added to the thermosetting resin composition of the present embodiment in order to prevent oxidation of the resin. Specific examples thereof include antioxidants such as hindered phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and copper-based antioxidants.

Known compounds can be used as the hindered phenolic antioxidant. These compounds can be used alone or in combination. Among such hindered phenolic antioxidants, bifunctional or higher functional phenols are preferable, and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245). Semi-hindered type such as is preferable in terms of resistance to discoloration.

The phosphorus-based antioxidant is at least one selected from inorganic and organic phosphorus-based antioxidants. Examples of the inorganic phosphorus-based antioxidant include hypophosphates such as sodium hypophosphate and phosphite. As the organic phosphorus-based antioxidant, a phosphite-based commercially available organic phosphorus-based antioxidant can be used, but an organophosphorus-containing compound that does not generate phosphoric acid by thermal decomposition is preferable. As such an organic phosphorus-containing compound, a known compound can be used.

A known amine-based antioxidant can be used in the thermosetting resin composition of the present embodiment. In addition, a secondary arylamine can also be mentioned as an amine-based antioxidant. The secondary arylamine means an amine compound containing two carbon radicals chemically bonded to a nitrogen atom, in which at least one, preferably both carbon radicals are aromatic.

A known sulfur-based antioxidant can be used in the thermosetting resin composition of the present embodiment.

In the thermosetting resin composition of the present embodiment, a copper-based antioxidant containing a mixture of a copper salt and a halide of an alkali metal and / or a halide of an alkaline earth metal can be used. For example, stabilizers including, but not limited to, a mixture of copper (I) iodide and potassium iodide.

By using a thermosetting resin composition containing any of the binder components (I) to (IV) and a heat conductive filler, highly reliable thermosetting with excellent electrical insulation, heat conductivity and dielectric properties A resin composition and a cured product thereof can be provided.

The thermally conductive resin composition is preferably produced by stirring and mixing a binder component and a thermally conductive filler with a solvent. A general stirring method can be used for stirring and mixing, and examples thereof include a scandex, a paint conditioner, a sand mill, a raft machine, a medialess disperser, a triple roll, and a bead mill, and these are combined. Can be done. The solvent here means a dispersion medium.

After stirring and mixing, it is preferable to go through a defoaming step in order to remove air bubbles from the thermally conductive resin composition. The defoaming method is not particularly limited and can be performed by using a general method, and examples thereof include vacuum defoaming and ultrasonic defoaming.

Various conventional additives can be added to the thermally conductive resin composition, if necessary. Examples of various additives include a coupling agent for enhancing the adhesion to the base material, a dispersant for enhancing the dispersibility of the heat conductive filler and the binder component, an ion scavenger for enhancing the insulation reliability during moisture absorption, and leveling. Agents and the like can be mentioned. One of these may be used, or a plurality of types may be used in combination.

The coating method is not particularly limited, and known methods can be used, for example, knife coat, die coat, lip coat, roll coat, curtain coat, bar coat, gravure coat, flexo coat, dip coat, spray coat. , Spin coat and the like. Alternatively, it may be poured into a mold and cast.

When the thermosetting resin composition is in the form of a sheet, a base material may be used as appropriate. As the base material, for example, a plastic film such as a polyester film, a polyethylene film, a polypropylene film, or a polyimide film, a film released from the plastic film (hereinafter referred to as a release film), or the like can be used. Further, metals such as aluminum, copper, stainless steel and beryllium copper, and foils of these alloys can be used as a base material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention at all. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, and Mw means the weight average molecular weight.

[Synthesis Example 1] <Styrene-based elastomer (P1) synthesis example>
In the block ratio of the polymer (hereinafter, the same applies), styrene: [ethylene / butylene] = 15: 85 (mass%), maleic anhydride 1.03 g, benzoyl to 100 g of a styrene elastomer (P1) having a weight average molecular weight of 55,000. 0.1 g of peroxide and 0.6 g of Irganox 1010 (antioxidant manufactured by BASF Japan) were dry-blended, further mixed using a 32 mm twin-screw extruder with a vent, melt-kneaded, and pelletized. A sample was obtained. The temperature of the twin-screw extruder during mixing and melt-kneading was 40 ° C. in the lower part of the hopper, 80 ° C. in the mixing zone, 170 ° C. in the reaction zone, and 180 ° C. in the die.
To 100 parts by mass of the obtained pellet-shaped sample, 85 parts by mass of acetone and 85 parts by mass of heptane were added, and the mixture was heated and stirred at 85 ° C. for 2 hours in a pressure resistant reactor. After completion of the same operation, pellets were collected with a wire mesh and vacuum dried at 140 ° C. and 0.1 Torr for 20 hours to obtain a styrene-butadiene block copolymer having an acid anhydride group. The molecular weight distribution is narrow, the weight average molecular weight 60000, the total acid number 11.2mgCH ₃ ONa / g, acid anhydride prices was 5.6mgCH ₃ ONa / g.

The Mw of Synthesis Example 1 was measured by using GPC (gel permeation chromatography) "HPC-8020" manufactured by Toso Co., Ltd. GPC is a liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified according to the difference in molecular size. In the measurement in the present invention, two "LF-604" (manufactured by Showa Denko: GPC column for rapid analysis: 6 mm ID x 150 mm size) are connected in series to the column, the flow rate is 0.6 mL / min, and the column temperature is 40. It was carried out under the condition of ° C., and the weight average molecular weight (Mw) was determined in terms of polystyrene.

The total acid value of Synthesis Example 1 is expressed by the amount (mg) of sodium methoxide required to neutralize the acid anhydride group and the carboxylic acid contained in 1 g of the resin solid. Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 mL of cyclohexanone solvent to dissolve it. Phenolphthalein test solution is added to this as an indicator and held for 30 seconds. Then titrate with 0.1N sodium methoxide solution until the solution turns pink. The acid value was calculated by the following formula (unit: mgCH ₃ ONa / g).
Acid value (mgCH ₃ ONa / g) = (5.412 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1 N sodium methoxide solution (mL)
F: Titer of 0.1N sodium methoxide solution

For the measurement of the acid anhydride price of Synthesis Example 1, about 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask, and 100 mL of a 1,4-dioxane solvent was added to dissolve the sample. Add 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mass mixing ratio is 1.49 / 800/80), which is larger than the amount of acid anhydride group in the sample, and stir for 15 minutes. It was reacted with the substance. Then, excess octylamine was titrated with a mixed solution of 0.02M perchloric acid and 1,4-dioxane. In addition, 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mass mixing ratio: 1.49 / 800/80) to which no sample was added was also measured as a blank. The acid anhydride price was calculated by the following formula (unit: mgCH ₃ ONa / g).
Acid anhydride price (mgCH ₃ ONa / g) = 0.02 x (BS) x F x 54.12 / W
B: Blank titration (mL)
S: Titration of sample (mL)
W: Sample solid amount (g)
F: 0.02 mol / L Perchloric acid titer

The ratio of the acid anhydride group of Synthesis Example 1 to the ring-opened carboxylic acid was determined by the following method.
Acid anhydride group: Ring-opened carboxylic acid = acid anhydride base value: (total acid value-acid anhydride base value x 2)

[Synthesis Example 2] <Synthesis Example of Polyamide Resin (P2)>
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer, 324.6 g of Pripol 1009 as a polybasic acid compound having 36 carbon atoms and a polybasic acid compound having a phenolic hydroxyl group were used. 25.7 g (0.14 mol) of 5-hydroxyisophthalic acid, 138.6 g of Wandamine HA, and 100 g of ion-exchanged water were charged, and the mixture was stirred until the exothermic temperature became constant. When the temperature became stable, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. 30 minutes later, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. .. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours and kept under a vacuum of about 2 kPa for 1 hour to lower the temperature. Finally, an antioxidant is added to the polyamide (A) having a weight average molecular weight of 21200, an acid value of 10.6 mgKOH / g, an amine value of 0.3 mgKOH / g, a phenolic hydroxyl value of 16.2 mgKOH / g, and a glass transition temperature of 50 ° C. -1) was obtained. The amount of the monomer having a C20 to 60 hydrocarbon group is 41.4 mol% in 100 mol% of all the monomers subjected to the reaction.

The phenolic hydroxyl value of Synthesis Example 2 is used to neutralize the amount of phenolic hydroxyl groups contained in 1 g of phenolic hydroxyl group-containing polyamide to acetic acid bonded to the phenolic hydroxyl groups when the phenolic hydroxyl groups are acetylated. It is expressed in terms of the required amount of potassium hydroxide (mg). The phenolic hydroxyl value was measured according to JIS K0070. In the present invention, when calculating the phenolic hydroxyl value of the phenolic hydroxyl group-containing polyamide of the terminal carboxylic acid, the acid value is taken into consideration as shown in the following formula.

The measurement of the phenolic hydroxyl value of Synthesis Example 2 was as follows.
Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 mL of cyclohexanone solvent to dissolve it. Further, exactly 5 mL of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 mL) was added, and the mixture was stirred for about 1 hour. Phenolphthalein TS is added as an indicator to this and lasts for 30 seconds. Then, titrate with 0.5N alcoholic potassium hydroxide solution until the solution turns pink.
The hydroxyl value was calculated by the following formula (unit: mgKOH / g).
Hydroxy group value (mgKOH / g)
= [{(B-a) x F x 28.05} / S] + D
However,
S: Sample collection amount (g)
a: Consumption of 0.5N alcoholic potassium hydroxide solution (mL)
b: Consumption (mL) of 0.5N alcoholic potassium hydroxide solution in the blank experiment
F: Titer of 0.5N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

The acid value of Synthesis Example 2 was determined by the following method.
Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 mL of cyclohexanone solvent to dissolve it. Phenolphthalein test solution is added to this as an indicator and held for 30 seconds. Then, titrate with 0.1N alcoholic potassium hydroxide solution until the solution turns pink. The acid value was calculated by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (mL)
F: Titer of 0.1N alcoholic potassium hydroxide solution

The amine value of Synthesis Example 2 was determined by the following method.
Weigh accurately about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 mL of cyclohexanone solvent to dissolve it. To this, add a few drops of an indicator prepared by separately mixing 0.20 g of Methyl Orange in 50 mL of distilled water and 0.28 g of Xylene Cyanol FF in 50 mL of methanol, and adding 30 drops. Hold for seconds. Then titrate with 0.1N alcoholic hydrochloric acid solution until the solution turns bluish gray. The amine value was calculated by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic hydrochloric acid solution (mL)
F: Titer of 0.1N alcoholic hydrochloric acid solution

The Mw of Synthesis Example 2 was determined by the following method. For the measurement of Mw, GPC (gel permeation chromatography) "GPC-101" manufactured by Showa Denko Corporation was used. GPC is a liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified according to the difference in molecular size. The measurement in the present invention uses two "KF-805L" (manufactured by Showa Denko: GPC column: 8 mm ID x 300 mm size) connected in series to the column, sample concentration 1 wt%, flow rate 1.0 ml / min, pressure. The measurement was performed under the conditions of 3.8 MPa and a column temperature of 40 ° C., and the weight average molecular weight (Mw) was determined in terms of polystyrene. For data analysis, the calibration curve, molecular weight, and peak area were calculated using the manufacturer's built-in software, and the mass average molecular weight was calculated with the retention time in the range of 17.9 to 30.0 minutes as the analysis target.

The method for measuring the glass transition temperature of the polyamide resin (P2) of Synthesis Example 2 was as follows. For the polyamide resin (P2) from which the solvent was dried and removed, a sample amount of about 5 mg was weighed in a standard aluminum container using "DSC-1" manufactured by Mettler Toledo, and the temperature modulation amplitude was ± 1 ° C. and the temperature modulation cycle was 60. The glass transition temperature was determined from the differential thermal curve of the reversible component by measuring from -80 to 200 ° C. under the condition of a temperature rise rate of 2 ° C./min for seconds.

[Synthesis Example 3] <Synthesis Example of Polyurethane Resin (P3)>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 352 parts of a diol having Mn = 1002 obtained from adipic acid and 3-methyl-1,5-pentanediol, and dimethylol. 32 parts of butanoic acid, 176 parts of isophorone diisocyanate, and 40 parts of toluene were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a solution of a urethane prepolymer having an isocyanate group at the terminal. Next, 810 parts of the obtained urethane prepolymer solution was added to a mixture of 32 parts of isophorone diamine, 4 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and 3 at 70 ° C. The reaction was carried out for a time to obtain a solution of a polyurethane polyurea resin having Mw = 35,000 and an acid value of 21 mgKOH / g. To this, 144 parts of toluene and 72 parts of 2-propanol were added to obtain a polyurethane polyurea resin solution having a solid content of 50%.

The Tg of Synthesis Example 3 was measured by differential scanning calorimetry (“DSC-1” manufactured by METTLER TOLEDO). Further, the measurement of Mw in Synthesis Example 3 was carried out in the same manner as in Synthesis Example 1. As for the acid value, 1 g of thermosetting resin was dissolved in 40 mL of methyl ethyl ketone, and the automatic titrator "AT-510" manufactured by Kyoto Denshi Kogyo Co., Ltd. was connected to "APB-510-20B" manufactured by the same company as a burette. .. Potentiometric titration was performed using a 0.1 mol / L ethanolic KOH solution as a titration reagent, and the number of mg of KOH per 1 g of resin was calculated.

[Synthesis Example 4] <Synthesis of Polyimide Resin (P4)>
378.7 g of dimerdiamine (priamine 1075) having 36 carbon atoms as a polyamine compound and bisphenol A as a tetracarboxylic dianhydride in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. 380.0 g of type acid dianhydride (4,4'- [propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride) (BISDA-1000) and 1100 g of cyclohexanone as a solvent were charged. , Stirred until uniform. After becoming uniform, the temperature was raised to 110 ° C., and after 30 minutes, the temperature was raised to 140 ° C., and when the temperature reached 140 ° C., the reaction was continued at the same temperature for 10 hours to continue the dehydration reaction. Next, an antioxidant was added to obtain a polyimide resin having a weight average molecular weight of 54,000, an acid value of 6.4 mgKOH / g, and an amine value of 0.3 mgKOH / g. The acid value, amine value, and weight average molecular weight of Synthesis Example 4 and Synthesis Examples 5 and 6 described later were determined by the same method as in Synthesis Example 2.

[Synthesis Example 5] <Synthesis of Polyimide Resin (P4)>
358.0 g of preamine 1075 as a polyamine compound and 3,3', 4,4'- as a tetracarboxylic dianhydride in a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer. 214.8 g of biphenyltetracarboxylic dianhydride (BPDA) and 823 g of xylene as a solvent were charged, and the mixture was stirred until uniform. When it became uniform, the temperature was raised to 110 ° C., and after 30 minutes, the temperature was raised to 140 ° C., and when the temperature reached 140 ° C., the reaction was continued at the same temperature for 10 hours to continue the dehydration reaction. Next, an antioxidant was added to obtain a polyimide resin having a weight average molecular weight of 16,000, an acid value of 4.3 mgKOH / g, and an amine value of 0.2 mgKOH / g.

[Synthesis Example 6] <Synthesis of Polyimide Resin (P4)>
371.6 g of preamine 1075 as a polyamine compound and 3,3', 4,4'- as a tetracarboxylic dianhydride in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. 226.5 g of diphenyl ether tetracarboxylic dianhydride (OPDA) and 860 g of xylene as a solvent were charged and stirred until uniform. When it became uniform, the temperature was raised to 110 ° C., and after 30 minutes, the temperature was raised to 140 ° C., and when the temperature reached 140 ° C., the reaction was continued at the same temperature for 10 hours to continue the dehydration reaction. Next, an antioxidant was added to obtain a polyimide having a weight average molecular weight of 30,000, an acid value of 8.1 mgKOH / g, and an amine value of 0.4 mgKOH / g.

[Preparation of sheet-shaped thermosetting resin composition] (Examples 1 to 17)
After mixing with a resin, a curing agent and a solvent (methyl ethyl ketone) at the blending ratio (parts by mass) shown in Table 1, a thermally conductive filler is added and stirred with a disper to have a solid content of 60% by mass. A thermosetting resin composition was obtained. Next, each of the thermosetting resin compositions of Examples 1 to 17 was applied onto a peelable sheet and dried to obtain a sheet 1 in which one side of the resin layer was covered with the peelable sheet. After that, another set of sheets 1 was obtained in the same manner, and the resin layer sides were overlapped with each other to form peelable sheets on both sides of the resin layer, that is, the laminated resin layers were sandwiched by the peelable sheets. A sheet-like thermosetting resin composition (hereinafter, also referred to as sheet 2) with a double-sided peelable sheet was formed.

[Relative permittivity]
The peelable sheet on one side of the sheet 2 of each example was removed and heat-cured at 180 ° C. for 1 hour, and then the peelable sheet on the opposite side was removed to prepare a test piece for evaluation. For this test piece, the relative permittivity and dielectric loss tangent at a measurement temperature of 23 ° C. and a measurement frequency of 5 GHz were determined by a cavity resonator method using a permittivity measuring device manufactured by AET.
A ... The relative permittivity is 3.2 or less.
B ... The relative permittivity is greater than 3.2 and 3.5 or less.
C ... The relative permittivity is greater than 3.5 and less than 4.0.
D ... The relative permittivity is greater than 4.0.

[Dissipation factor]
A ... The dielectric loss tangent is 0.003 or less.
B ... The dielectric loss tangent is greater than 0.003 and less than 0.005.
C ... The dielectric loss tangent is greater than 0.005 and 0.010 or less.
D ... The dielectric loss tangent is greater than 0.010.

[Thermal conductivity]
<Thermal conductivity>
The side of the sheet 1 of each example that was not covered with the peelable sheet was covered with the same peelable sheet as described above, and heat-pressed at 180 ° C. for 1 hour at a pressure of 1 MPa. Then, the peelable sheets on both sides were peeled off to obtain a single-layer thermal conductive sheet (hereinafter referred to as a measurement sample). The obtained measurement sample was cut into 15 mm squares, and the surface of the measurement sample was vapor-deposited with gold and coated with carbon spray. Next, the thermal diffusivity at a sample environment of 25 ° C. was measured with a xenon flash analyzer LFA447Nano Flash (manufactured by NETZSCH). The specific heat capacity was measured using a high-sensitivity differential scanning calorimeter DSC220C manufactured by SII Nanotechnology Co., Ltd. Furthermore, the density was calculated using the underwater substitution method. For the thermal conductivity, the thermal conductivity was determined based on the following formula, and the result was judged according to the following criteria.
Conductivity (W / m · K) = Density (g / cm ³ ) x Specific heat (J / kg · K) x Thermal diffusivity (mm ² / s).
A ... The thermal conductivity is 5 W / m · K or more.
B ... The thermal conductivity is 2 W / m · K or more and less than 5 W / m · K.
C ... The thermal conductivity is 0.5 W / m · K or more and less than 2 W / m · K.
D: Thermal conductivity is less than 0.5 W / m / K.

<Adhesiveness>
The sheet 2 of each example is cut into a size of 65 mm × 65 mm, a peelable sheet on one side is removed, and the sheet 2 is bonded to a polyimide film [“Kapton 300H” manufactured by Toray DuPont Co., Ltd.] having a thickness of 75 μm. After that, the other peelable sheet was removed, laminated with a copper-clad laminate having a thickness of 45 μm, laminated at 80 ° C., and then pressure-bonded at 160 ° C. and 1.0 MPa for 5 minutes. Further, this test piece was heat-cured at 160 ° C. for 1 hour to prepare a test piece for evaluation. This test piece was cut into a width of 10 mm and a length of 65 mm, and a T-peel peeling test was performed at a tensile speed of 300 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%, and the adhesive strength (N / cm) was measured. This test evaluates the adhesive strength of the cured product of the thermosetting resin composition for heat conductive materials when used at room temperature, and the results were judged according to the following criteria.
A: The adhesive strength is 15 (N / cm) or more.
B ... Adhesive strength is 10 (N / cm) or more and less than 15 (N / cm) C ... Adhesive strength is 5 (N / cm) or more and less than 10 (N / cm).
D ... Adhesive strength is less than 5 (N / cm).

The curing agents and the like used in this example are as follows.
(Hardener)
-Curing agent 1: TETRAD-X, manufactured by Mitsubishi Gas Chemicals, a tetrafunctional polyfunctional glycidylamine compound-Curing agent 2: 24A-100: Biuret of hexamethylene diisocyanate (hereinafter abbreviated as HDI) manufactured by Asahi Kasei Chemicals. Hardener 3: ZC700, manufactured by Matsumoto Fine Chemical Co., Ltd., 4-functional Zr chelate compound / hardener 4: Epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., JER1031S
(Thermal conductive filler)
Boron Nitride Nitride: PTX60: Granulated boron nitride filler (Momentive PTX-60) having an average compressive force of 3.6 mN and an average particle size of 55 to 65 μm for a compressive deformation rate of 10%.
Alumina: ao509: Spherical alumina having an average circularity of 0.99 and an average particle diameter of 10 μm (Admafine AO-509 manufactured by Admatex),
(Other fillers)
-PTFE: PTFE "CERAFLOUR 981 (average particle size D50: 3 μm)" manufactured by Big Chemie (flame retardant)
-Flame retardant 1: Aluminum phosphinate

[Additional Notes]
The present specification also discloses inventions of the following technical ideas grasped from the above embodiments.
(Appendix 1)
An anisotropic conductive adhesive made by adding a conductive filler to a thermosetting resin composition for a heat conductive material containing a binder component containing a thermosetting resin and a curing agent and a heat conductive filler.
The binder component is
A binder component (I) containing a styrene-based elastomer (P1) having an anhydride group of a carboxylic acid and a polyisocyanate component (C1) that reacts with the anhydride group.
A binder component (II) containing a polyamide resin (P2) having a phenolic hydroxyl group as a side group and a trifunctional or higher functional compound (C2) capable of reacting with the phenolic hydroxyl group, or a polyurethane resin having a carboxyl group (P3). ) And an epoxy compound (C3) capable of reacting with the carboxyl group, which is a binder component (III).
The cured product after curing the thermosetting resin composition for a heat conductive material is
The relative permittivity is 4.0 or less at a frequency of 5 GHz and 23 ° C.
Dissipation factor is 0.010 or less at a frequency of 5 GHz and 23 ° C.
An anisotropic conductive adhesive.

Claims (9)

A thermosetting resin composition for a heat conductive material containing a binder component containing a thermosetting resin and a curing agent and a heat conductive filler.
The binder component is
A binder component (I) containing a styrene-based elastomer (P1) having an anhydride group of a carboxylic acid and a polyisocyanate component (C1) that reacts with the anhydride group.
A binder component (II) containing a polyamide resin (P2) having a phenolic hydroxyl group as a side group, a trifunctional or higher functional compound (C2) capable of reacting with the phenolic hydroxyl group, and a polyurethane resin (P3) having a carboxyl group. And a binder component (III) containing an epoxy compound (C3) capable of reacting with the carboxyl group, or a polyimide resin (P4) having a reactive functional group and containing a hydrocarbon group having 20 to 60 carbon atoms. , A binder component (IV) containing a bifunctional or higher functional compound (C4) that reacts with the reactive functional group.
The cured product after curing the thermosetting resin composition for the heat conductive material is
The relative permittivity is 4.0 or less at a frequency of 5 GHz and 23 ° C.
Dissipation factor is 0.010 or less at a frequency of 5 GHz and 23 ° C.
Thermosetting resin composition for heat conductive materials. Styrene-based elastomer (P1)
It is a block copolymer having at least one of a structural unit derived from an olefin and a structural unit derived from a conjugated diene, and a structural unit derived from styrene, and the polyisocyanate component (C1) has two or more isocyanates. Isocyanate group-containing compound
Polyamide resin (P2) is
The following (i) and / or (ii), further, the polyamide resin (P2) of (i) satisfies (iii) and (vi), and the polyamide resin (P2) of (ii) is (iv). Satisfying ~ (vi),
Compound (C2) satisfies the following (vii).
The polyurethane resin (P3) is a polyurethane polyurea resin.
The polyimide resin (P4) contains a structural unit derived from an aromatic carboxylic acid polyanhydride and a structural unit derived from a polyamine compound having a hydrocarbon group having 20 to 60 carbon atoms, and the hydrocarbon group having 20 to 60 carbon atoms. More than 70% by mass of the group is derived from the hydrocarbon skeleton.
The reactive functional groups are amine and / and acid anhydride groups.
The thermosetting resin composition for a heat conductive material according to claim 1, wherein the bifunctional or higher functional compound (C4) is an epoxy compound.
(I) The polyamide resin (P2) is a polyamide (A) containing the phenolic hydroxyl group and a hydrocarbon group having 20 to 60 carbon atoms (however, the aromatic ring to which the phenolic hydroxyl group is bonded is not included) in the same polymer. -1).
(Ii) The polyamide resin (P2) is a polyamide (A-1) in which a polyamide (a-1) containing a phenolic hydroxyl group as a side group and a polyamide (a-2) containing a hydrocarbon group having 20 to 60 carbon atoms are mixed. -3).
(Iii) As the monomer constituting the polyamide (A-1), a monomer having a phenolic hydroxyl group and a monomer having a hydrocarbon group having 20 to 60 carbon atoms are included.
(Iv) The polybasic acid monomer and / and the polyamine monomer constituting the polyamide (a-1) contain a monomer having a phenolic hydroxyl group, and the polybasic acid monomer and the polyamine The monomer does not contain a monomer having a hydrocarbon group having 20 to 60 carbon atoms.
(V) The polybasic acid monomer and / and the polyamine monomer constituting the polyamide (a-2) contain a monomer having a hydrocarbon group having 20 to 60 carbon atoms, and the polyamine is added. The basic acid monomer and the polyamine monomer do not contain a monomer having a phenolic hydroxyl group.
(Vi) At least a part of the monomer having a hydrocarbon group having 20 to 60 carbon atoms contains a compound having a cyclic structure having 5 to 10 carbon atoms.
The (vii) compound (C2) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, a carbodiimide group-containing compound, a metal chelate, a metal alkoxide, and a metal acylate. As the thermal conductive filler, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, zinc oxide, beryllium oxide, aluminum oxide, aluminum nitride, boron nitride, molten silica, etc. The thermocurable resin composition for a heat conductive material according to claim 1 or 2, which is at least one selected from the group consisting of crystalline silica, non-crystalline silica, silicon carbide, silicon nitride, titanium carbide, and diamond. The thermosetting resin composition for a heat conductive material according to any one of claims 1 to 3, which is any of powder, film, sheet, plate, pellet, paste and liquid. A cured product of a thermosetting resin composition for a heat conductive material, which is obtained by curing the thermosetting resin composition for a heat conductive material according to any one of claims 1 to 4. An electronic component comprising a cured product of the thermosetting resin composition for a heat conductive material according to claim 5. The electronic component according to claim 6, wherein the cured product is a circuit board or an insulating layer formed on the circuit board. The electronic component according to claim 6, wherein the cured product is used as an adhesive or a sealing material. An electronic device equipped with the electronic component according to any one of claims 6 to 8.