WO2013065159A1

WO2013065159A1 - Resin composition, and resin sheet, prepreg, laminate, metal substrate and printed circuit board using same

Info

Publication number: WO2013065159A1
Application number: PCT/JP2011/075345
Authority: WO
Inventors: 優香吉田; 竹澤　由高; 靖夫宮崎; 高橋　裕之
Original assignee: 日立化成株式会社
Priority date: 2011-11-02
Filing date: 2011-11-02
Publication date: 2013-05-10
Also published as: JP5928477B2; CN110128786A; JPWO2013065159A1; KR20140087012A; CN103917605A; KR101780536B1

Abstract

A resin composition comprising: a first filler having an average particle diameter (D50) of 1 nm to 500 nm corresponding to 50% cumulation from the smallest particle diameter side in a weight cumulative particle size distribution, and including α-alumina; a second filler having an average particle diameter (D50) of 1 μm to 100 μm corresponding to 50% cumulation from the smallest particle diameter side in a weight cumulative particle size distribution; and a thermosetting resin including a mesogenic group within each molecule.

Description

Resin composition, and resin sheet, prepreg, laminate, metal substrate and printed wiring board using the same

The present invention relates to a resin composition, and a resin sheet, prepreg, laminate, metal substrate and printed wiring board using the same.

Many electronic and electrical devices ranging from motors and generators to printed wiring boards and IC chips are composed of a conductor for conducting electricity and an insulating material. In recent years, since the amount of heat generation has increased with the miniaturization of these devices, how to dissipate heat in insulating materials has become an important issue.

As the insulating material used in these devices, a cured resin material made of a resin composition is widely used from the viewpoint of insulation and heat resistance. However, since the thermal conductivity of the cured resin is generally low and is a major factor hindering heat dissipation, development of a cured resin having high thermal conductivity is desired.

As a method for achieving high thermal conductivity of a cured resin product, there is a method of filling a resin composition with a thermal conductive filler made of a high thermal conductive ceramic to form a composite material. As high thermal conductive ceramics, boron nitride, alumina, aluminum nitride, silica, silicon nitride, magnesium oxide, silicon carbide and the like are known. By filling the resin composition with a thermally conductive filler that achieves both high thermal conductivity and electrical insulation, it is possible to achieve both high thermal conductivity and insulation in the composite material.

In relation to the above, Japanese Patent Application Laid-Open No. 2009-13227 discloses that electrical insulation and thermal conductivity are good by adding a small amount of nanoparticle-sized inorganic filler in addition to the microparticle-sized thermal conductive filler. It has been reported that a resin composition for an electrically insulating material was obtained.

Furthermore, as a technique for achieving high thermal conductivity of a cured resin product, a method for increasing the thermal conductivity of the resin itself by orderly arranging monomers having mesogenic groups in the molecule has been studied. As an example of such a monomer, an epoxy resin monomer as shown in Japanese Patent No. 4118691 has been proposed.

Here, as an aspect of the insulating material disposed in the electrical equipment, a fiber base material such as a woven fabric or a non-woven fabric is used for the purpose of improving dimensional stability, mechanical strength, etc., and the resin composition is used for the fiber base material. A prepreg may be produced by impregnating an object. The impregnation method of the fiber base material of the resin composition includes a vertical coating method in which the fiber base material is pulled through the resin composition, and the fiber base material is pressed after the resin composition is applied onto the support film. There is a horizontal coating method to impregnate. In the case of using the resin composition containing the filler as described above, a horizontal coating method is often applied in consideration of sedimentation of the filler, in which variation in composition is less likely to occur in the fiber base material.

In the resin composition filled with the above-mentioned heat conductive filler having a microparticle size, it is necessary to increase the filling amount of the filler in order to realize the high thermal conductivity that has been required in recent years. In a resin composition highly filled with a filler, the viscosity increases remarkably due to the interaction between the filler surface and the resin, which may easily enclose air bubbles by entraining air. Moreover, since the frequency with which fillers are fitted increases, fluidity may be significantly reduced. As a result, the resin composition highly filled with the filler is difficult to eliminate voids due to poor embedding of the surface structure of the adherend and air bubbles generated during coating. It tends to cause dielectric breakdown due to pores / bubbles.

In addition, when a prepreg is produced by impregnating a fiber base material with a resin composition, if the amount of filler in the resin composition is large, the filler fits into the fiber and clogs, and the resin is sufficiently stained from the surface of the fiber base material. It may not come out or may not fill the gap between the fibers and leave holes. Furthermore, when the resin bleeds from the surface of the fiber substrate is insufficient, the adhesive strength of the prepreg to the adherend may be insufficient, causing interfacial peeling. Furthermore, the pores in the adherend interface and the fiber substrate may cause a decrease in insulation.

Here, in order to improve the fluidity of the resin composition filled with the filler, generally, (1) a method of lowering the viscosity of the resin, and (2) a surface treatment of the filler or addition of a dispersant is constrained on the filler surface. There is a method of reducing the amount of resin to be obtained.

However, simply lowering the viscosity of the resin improves the seepage of the resin itself from the fiber substrate surface, but does not improve the fit between the filler and the fiber. Therefore, there is a problem that only the resin oozes out from the surface of the fiber base material while leaving the filler on the fiber, and further, if the pressure is too high, only the resin oozes out and forms a defect such as a void. . In addition, the viscosity of the resin composition has decreased too much, causing sedimentation of the filler in the thickness direction of the coating film of the resin composition, resulting in a distribution of the density of the filler in the thickness direction of the coating film. .

On the other hand, when the fluidity of the resin composition is improved only by the surface treatment of the filler and the addition of a dispersant, the filler coverage of the surface treatment and the addition of a dispersant are added so that the resin can be sufficiently oozed out from the surface of the fiber substrate. When the amount is increased, chemical bonding between the filler and the resin is inhibited, and there is a problem that the thermal conductivity as the composite material is lowered.

In addition, in order to increase the thermal conductivity of the resin composition by orderly arranging monomers having mesogenic groups in the molecule, the monomers having mesogenic groups are generally easy to crystallize and are solid at room temperature, so compared with general-purpose resins. May be difficult to handle. Further, when the filler is highly filled, the above-described difficulty is added, and thus molding may become more difficult.

As a method for solving the above-mentioned problem, there is a method of adding a small amount of nano-sized inorganic filler. Under the conditions shown in Japanese Patent Application Laid-Open No. 2009-13227, although the dielectric breakdown property is improved, the thermal conductivity is not yet achieved. The result was lower than that of the additive.

Under such circumstances, an object of the present invention is to provide a resin composition that can achieve both excellent thermal conductivity and excellent fluidity. It is another object of the present invention to provide a resin sheet, a prepreg, a laminate, a metal substrate, and a printed wiring board that are configured using the resin composition and have excellent thermal conductivity and excellent insulation.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention includes the following aspects.
<1> The average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution is 1 nm to 500 nm, the first filler containing α-alumina, and the small weight cumulative particle size distribution A resin composition comprising a second filler having an average particle diameter (D50) corresponding to a cumulative 50% from the particle diameter side of 1 μm to 100 μm, and a thermosetting resin having a mesogenic group in the molecule.

<2> The resin composition according to <1>, wherein the content of the first filler is 0.1% by volume to 10% by volume in the entire volume.

<3> The second filler is the resin composition according to <1> or <2>, including a nitride filler.

<4> The resin composition according to <3>, wherein the nitride filler includes at least one selected from the group consisting of boron nitride and aluminum nitride.

<5> The resin composition according to any one of <1> to <4>, wherein the content of the second filler is 55% to 85% by volume in the entire volume.

<6> The resin composition according to any one of <1> to <5>, wherein the thermosetting resin is an epoxy resin.

<7> The resin composition according to any one of <1> to <6>, wherein the mesogenic group has a structure in which three or more six-membered ring groups are connected in a straight chain.

<8> The resin composition according to any one of <1> to <7>, further including a phenol novolac resin.

<9> The above-mentioned <8>, wherein the phenol novolak resin is a novolak resin containing a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (I-1) and (I-2) >.

In general formulas (I-1) and (I-2), R ¹ independently represents an alkyl group, an aryl group, or an aralkyl group. R ² and R ³ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Each m independently represents an integer of 0 to 2, and each n independently represents an integer of 1 to 7.

<10> The phenol novolak resin is the resin composition according to <8> or <9>, wherein a content ratio of a monomer composed of a phenol compound constituting the phenol novolak resin is 5% by mass to 80% by mass. .

<11> A semi-cured resin composition that is a semi-cured body of the resin composition according to any one of <1> to <10>.

<12> A cured resin composition that is a cured product of the resin composition according to any one of <1> to <10>.

<13> A resin sheet which is a sheet-like molded body of the resin composition according to any one of <1> to <10>.

<14> The resin sheet according to <13>, wherein a flow amount in a semi-cured state is 130% to 210%.

<15> A prepreg having a fiber base material and the resin composition according to any one of <1> to <10> impregnated in the fiber base material.

<16> Adhering material, the resin composition according to any one of <1> to <10>, and the resin sheet according to <13> and <14>, disposed on the adhering material And a laminate having at least one semi-cured resin composition layer selected from the group consisting of the prepregs described in <15>, or a cured resin composition layer that is a cured body.

<17> Metal foil, the resin composition according to any one of <1> to <10>, the resin sheet according to <13> and <14>, and the prepreg according to <15> A cured resin composition layer that is at least one cured body selected from the above and a metal plate are laminated metal substrates in this order.

<18> A metal plate, the resin composition according to any one of <1> to <10>, the resin sheet according to <13> and <14>, and the prepreg according to <15>. A printed wiring board in which a cured resin composition layer that is at least one cured body selected from the above and a wiring layer are laminated in this order.

According to the present invention, it is possible to provide a resin composition that can achieve both excellent thermal conductivity and excellent fluidity. In addition, a resin sheet, a prepreg, a laminate, a metal substrate, and a printed wiring board that are configured using the resin composition and have excellent thermal conductivity and excellent insulation can be provided.

It is a schematic sectional drawing which shows notionally an example of a structure of the cured resin composition concerning this embodiment. It is a schematic sectional drawing which shows notionally an example of a structure of the cured resin composition concerning the comparative example 1. It is a schematic sectional drawing which shows notionally an example of a structure of the cured resin composition concerning Comparative Examples 2 and 4. It is a schematic sectional drawing which shows notionally an example of a structure of the cured resin composition concerning the comparative example 5.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. . In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.

<Resin composition>
The resin composition of the present invention has an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution of 1 nm to 500 nm, a first filler containing α-alumina, A second filler having an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the cumulative particle size distribution, and a thermosetting resin having a mesogenic group in the molecule, If necessary, it further comprises other components.
With this configuration, both excellent thermal conductivity and excellent fluidity can be achieved.

By using a thermosetting resin having a mesogenic group in the molecule and a first filler having a specific average particle size including α-alumina, the thermal conductivity of the cured resin composition is dramatically improved. . It is described in Japanese Patent No. 4118691 that a cured product of a thermosetting resin having a mesogenic group in the molecule is excellent in thermal conductivity. However, when the thermosetting resin is used in combination with an α-alumina filler having a specific average particle size, the thermal conductivity of the cured resin composition is improved beyond the expectation described in Japanese Patent No. 4118691. This can be considered, for example, to be due to the formation of a high-order structure of a thermosetting resin having high ordering on the surface of the α-alumina filler, which is a nanoparticle.

Furthermore, in the present invention, since the average particle diameter of the first filler is smaller than the average particle diameter of the second filler, the thermal conductivity of the cured resin composition is greatly improved. Specifically, a cured resin is obtained by combining a second filler having an average particle diameter (D50) of 1 μm to 100 μm and a first filler having an average particle diameter (D50) containing α-alumina of 1 nm to 500 nm. The thermal conductivity of the composition is greatly improved. For example, the present inventors consider as follows. However, the present invention is not limited to the following estimation mechanism.

Usually, in the cured resin composition comprising a filler and a resin, the resin exists at the interface between the fillers. Since the resin has a lower thermal conductivity than the filler, it becomes difficult for heat to be transferred between the fillers. Therefore, no matter how high the filler is filled and the fillers are brought into close contact with each other, heat conduction is largely lost at the filler interface. On the other hand, in the cured resin composition of the present invention, the thermosetting resin having mesogenic groups in the molecules existing between the fillers efficiently transfers heat, and further the thermosetting having mesogenic groups in the first filler and molecules. By combining the heat-resistant resin, the thermal conductivity between the first filler and between the first filler and the second filler is further improved, so there is less loss of heat conduction at the filler interface, resulting in a cured resin composition. It is thought that the thermal conductivity of the is improved.
This estimation mechanism will be further described with reference to the drawings.

FIG. 1 is a cross-sectional view conceptually showing the cured resin composition according to this embodiment, and schematically shows an arrow heat conduction path in FIG. As shown in FIG. 1, the first filler 20 has a smaller average particle diameter than the second filler 10, and thus can enter a gap formed between the second fillers 10 in the cured resin composition. it can. Further, on the surface of the first filler 20, a cured product 30 made of a thermosetting resin having a mesogenic group forms a higher order structure as shown in the enlarged view of FIG. Thereby, the 1st filler 20 in which the higher-order structure of the resin hardened | cured material 30 was formed in the surface comprises the new heat conduction path | route which connects 2nd fillers 10 mutually. As a result, an efficient heat conduction path in the cured resin composition is increased, and a higher heat conductivity can be obtained.

FIG. 2 is a sectional view conceptually showing a cured resin composition according to Comparative Example 1 described later, and the arrows in FIG. 2 schematically show the heat conduction paths as in FIG. In the cured resin composition composed of the second filler 10 and the cured product 30 composed of a thermosetting resin having a mesogenic group, as shown in FIG. 2, the gap formed between the second fillers 10 is increased. It is filled with the cured resin 30 having the next structure. Although the cured resin 30 having a higher order structure has higher thermal conductivity than a general cured resin, the first structure in which the higher order structure of the cured resin 30 having a mesogenic group on the surface in FIG. 1 is formed. Compared with the filler 20, thermal conductivity is lowered. Therefore, it is considered that the cured resin composition as shown in FIG. 2 has lower thermal conductivity than the cured resin composition as shown in FIG.

On the other hand, FIG. 3 is a sectional view conceptually showing a cured resin composition according to Comparative Examples 2 and 4 to be described later, and the arrows in FIG. 3 schematically show the heat conduction paths as in FIG. . As shown in FIG. 3, a thermosetting having a filler 40 (for example, silica filler or γ-alumina filler) having an average particle diameter (D50) other than α-alumina of 1 nm to 500 nm, a second filler 10 and a mesogenic group. In the cured resin composition composed of the cured product 30 made of the functional resin, the gap formed between the second fillers 10 is high with the filler 40 having an average particle diameter (D50) other than α-alumina of 1 nm to 500 nm. It is filled with the cured resin 30 having the next structure. With the filler 40 having an average particle size (D50) other than α-alumina (D50) of 1 nm to 500 nm and the cured resin 30 having a higher order structure, the higher order structure of the cured resin 30 having a mesogenic group on the surface in FIG. 1 is formed. Compared with the made first filler 20, the thermal conductivity is lowered. Therefore, it is considered that the cured resin composition as shown in FIG. 3 has a lower thermal conductivity than the cured resin composition as shown in FIG.

Further, FIG. 4 is a cross-sectional view conceptually showing a cured resin composition according to Comparative Example 5 described later, and the arrows in FIG. 4 schematically show the heat conduction paths as in FIG. As shown in FIG. 4, in the cured resin composition composed of the first filler 20, the second filler 10, and a cured product 50 made of a thermosetting resin having no mesogenic group, the second filler 10 The gap formed between the first filler 20 and the cured resin 50 that does not form a higher order structure is filled. The first filler 20 and the cured resin 50 that does not form a higher order structure are more thermally conductive than the first filler 20 in which the higher order structure of the cured resin 30 having a mesogenic group is formed on the surface in FIG. Decreases. Therefore, in the cured resin composition as shown in FIG. 4, it is thought that thermal conductivity falls compared with a cured resin composition as shown in FIG.

Here, the higher-order structure is a higher-order structure in which the constituent elements are arranged in a micro array, and corresponds to, for example, a crystal phase or a liquid crystal phase. The presence confirmation of such a higher-order structure can be easily determined by observation with a polarizing microscope. That is, in the observation in the crossed Nicols state, it can be distinguished by seeing interference fringes due to depolarization.

This higher order structure usually exists in the form of islands in the resin and refers to that one island that forms a domain structure. This higher order structural unit generally has a covalent bond.

In addition, by using a thermosetting resin having a mesogenic group in the molecule as the thermosetting resin, the present inventors can form a higher order structure of a cured resin product having high order on the first filler surface. I found out. Furthermore, it has been found that the thermosetting resin having a mesogenic group exhibits higher order with the first filler as a nucleus, and the thermal conductivity of the cured resin itself is improved. In the cured resin composition in the present invention, the first filler in which the higher-order structure of the cured resin having a mesogenic group is formed on the surface enters the gaps between the second fillers, and increases the heat conduction path. High thermal conductivity can be obtained.
The presence of the higher order structure of the cured resin on the first filler surface can be found as follows.

A cured product (thickness: 0.1 μm to 20 μm) of a thermosetting resin having a mesogenic group containing 5% by volume to 10% by volume of the first filler is used with a polarizing microscope (eg, Olympus BX51). When observed, an interference pattern was observed around the filler, and no interference pattern was observed in the region where no filler was present. From this, it can be seen that the cured resin having a mesogenic group centering on the filler forms a higher order structure. Note that the observation needs to be performed not in the crossed Nicols state but in a state where the analyzer is rotated by 60 ° with respect to the polarizer. In the crossed Nicol state, a region where no interference pattern is observed (that is, a region where the resin does not form a higher order structure) becomes a dark field, and cannot be distinguished from the filler portion. However, by rotating the analyzer by 60 ° with respect to the polarizer, the region where the interference pattern is not observed is not a dark field, and can be distinguished from the filler portion.
The above phenomenon can be observed not only with the first filler but also with a high thermal conductivity ceramic filler such as boron nitride, alumina, aluminum nitride, silica, etc. Even if (D50) is outside the range of the first filler, the area of the interference pattern formed around the filler is extremely large.

The resin composition contains a first filler having a specific average particle diameter (D50) and a second filler in combination. The average particle diameter (D50) in the present invention means a particle diameter at which accumulation is 50% when a weight cumulative particle size distribution is drawn from the small particle diameter side.

Here, the weight cumulative particle size distribution is measured using a laser diffraction method. The particle size distribution measurement using the laser diffraction method can be performed using a laser diffraction scattering particle size distribution measuring apparatus (for example, LS13 manufactured by Beckman Coulter, Inc.). When the filler is an organic solvent dispersion, the filler dispersion for measurement is diluted with the same organic solvent so that the amount of light is appropriate for the sensitivity of the apparatus. When the filler is a powder, the powder is put into a 0.1% by mass sodium metaphosphate aqueous solution, ultrasonically dispersed, and measured at a concentration that provides an appropriate amount of light for the sensitivity of the apparatus.

Lubricating effect between the second fillers having an average particle diameter (D50) of 1 μm to 100 μm contained in the resin composition by adding the first filler having an average particle diameter (D50) of 1 nm to 500 nm to the resin composition Needless to say, in the prepreg in which the fiber base material is impregnated with the resin composition, a lubricating effect between the second filler and the fiber base material can be obtained.

In the resin sheet and resin-coated metal foil formed using such a resin composition having excellent fluidity, it is possible to satisfactorily fill the pores formed during the production and the voids with the interface of the adherend, Improves dielectric breakdown. Further, in the prepreg formed by impregnating the fiber base material with this resin composition, the second filler can be satisfactorily slipped in the gaps of the fiber base material, and the resin composition has a good fiber base. Since the material oozes out from the material and can fill well the inside of the base material and the interface with the adherend at the time of application, the dielectric breakdown property is improved. Furthermore, due to the good fluidity, when hot pressing is performed after coating, the resin can be oozed out to the surface of the fiber substrate, and the adhesiveness is also improved.

Since the resin composition is excellent in thermal conductivity and fluidity, a laminate, a metal substrate, and a printed wiring board having an insulating layer obtained by curing the resin composition exhibit higher thermal conductivity and insulation. The
Hereinafter, the material used for the resin composition and the physical properties of the resin composition will be described.

(First filler)
The resin composition includes a first filler having an average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution of 1 nm to 500 nm and containing α-alumina.
The average particle diameter (D50) of the first filler is preferably 50 nm to 450 nm, more preferably 100 nm to 450 nm, from the viewpoint of improving thermal conductivity and fluidity.

When the average particle diameter (D50) of the first filler exceeds 500 nm, the first filler cannot sufficiently enter the gap between the second filler, and as a result, the filling amount of the entire filler in the resin composition However, the thermal conductivity tends to decrease. Moreover, if the average particle diameter (D50) of a 1st filler is less than 1 nm, the lubricity between 2nd fillers or between a 2nd filler and a fiber base material may not fully be obtained.
The method for obtaining the average particle size of the first filler is as described above.

The first filler contains α-alumina. When α-alumina is not included, sufficient thermal conductivity may not be obtained. In addition, by containing α-alumina, a resin composition having a high melting point, high mechanical strength, and electrical insulation can be obtained, and the filling property of the first filler is improved.

The first filler may further contain alumina other than α-alumina as required. Of these, alumina other than α-alumina is preferably a round filler. Examples of alumina other than α-alumina include γ-alumina, θ-alumina, and δ-alumina, but it is preferably composed only of α-alumina.

The presence of α-alumina in the first filler can be confirmed by an X-ray diffraction spectrum. Specifically, for example, according to the description in Japanese Patent No. 3759208, the presence of α-alumina can be confirmed using a peak peculiar to α-alumina as an index.

The content rate of the 1st filler contained in the said resin composition is not restrict | limited in particular. The first filler is preferably contained in an amount of 0.1% by volume to 10% by volume in the total volume of the total solid content of the resin composition. In the resin composition, when the first filler is contained in an amount of 0.1 to 10% by volume in the entire volume, the lubricity between the second filler and between the second filler and the fiber substrate is further improved. The effect which raises and raises the heat conductivity of a resin composition more is acquired.
The content of the first filler is preferably 0.2% by volume to 10% by volume, and more preferably 0.2% by volume to 8% by volume from the viewpoint of improving thermal conductivity and fluidity. .
Here, the total solid content of the resin composition means a residue obtained by removing volatile components from the resin composition.

In addition, let the content rate (volume%) of the 1st filler in this specification be the value calculated | required by following Formula.

Content of first filler (volume%) = (Aw / Ad) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd) + (Ew / Ed))) × 100

Here, each variable is as follows.
Aw: Mass composition ratio (% by mass) of the first filler
Bw: mass composition ratio (mass%) of the second filler
Cw: mass composition ratio of thermosetting resin (mass%)
Dw: mass composition ratio of curing agent (mass%)
Ew: Mass composition ratio (% by mass) of other optional components (excluding organic solvents)
Ad: Specific gravity of the first filler Bd: Specific gravity of the second filler Cd: Specific gravity of the thermosetting resin Dd: Specific gravity of the curing agent Ed: Specific gravity of other optional components (excluding organic solvents)

The first filler can be used singly or in combination of two or more. For example, different α-alumina having an average particle diameter (D50) in the range of 1 nm to 500 nm can be used in combination, but is not limited to this combination.

The first filler may have a single peak or a plurality of peaks when a particle size distribution curve having a particle diameter on the horizontal axis and a frequency on the vertical axis is drawn. Good. By using the first filler having a plurality of peaks in the particle size distribution curve, the filling property between the second fillers is further improved, and the thermal conductivity as the cured resin composition is improved. The first filler having a plurality of peaks in the particle size distribution curve can be constituted by combining two or more first fillers having different average particle diameters (D50), for example.

Regarding the combination of the first filler, for example, when combining two types of alumina having different average particle diameters (D50), the filler (a) having an average particle diameter (D50) of 250 nm to 500 nm, and It is a mixed filler with a filler (b) whose average particle diameter (D50) is ½ or less of the filler (a) and is 1 nm or more and less than 250 nm, and the filler (a) with respect to the total volume of the first filler Is preferably 90 to 99% by volume, and filler (b) is preferably 1 to 10% by volume (provided that the total volume% of fillers (a) and (b) is 100% by volume). It is.

(Second filler)
The resin composition contains at least one second filler having an average particle diameter (D50) determined from a weight cumulative particle size distribution of 1 μm to 100 μm.

The second filler has a higher thermal conductivity than the cured resin of the curable resin, and is not particularly limited as long as the average particle diameter (D50) is 1 μm to 100 μm. Usually, for improving the thermal conductivity Appropriate selections can be made from those used as fillers. The second filler is preferably electrically insulating.

The thermal conductivity of the second filler is not particularly limited as long as it is higher than the cured resin. For example, the thermal conductivity is preferably 1 W / mK or more, and more preferably 10 W / mK or more.

Specific examples of the second filler include boron nitride, aluminum nitride, alumina, silica, and magnesium oxide. From the viewpoint of further improving the thermal conductivity, a nitride filler is preferable, and among them, at least one of boron nitride and aluminum nitride is preferable.

The second filler can be used singly or in combination of two or more. For example, boron nitride and aluminum nitride can be used in combination, but are not limited to this combination.

The content of the second filler is not particularly limited, but it is preferably contained at 55 volume% to 85 volume% in the total volume of the total solid content of the resin composition. When the content of the second filler in the resin composition is 55% by volume or more, the thermal conductivity is more excellent. Moreover, a moldability and adhesiveness improve that it is 85 volume% or less. The content of the second filler in the present invention is more preferably 60% by volume to 85% by volume in the total volume of the total solid content of the resin composition from the viewpoint of increasing the thermal conductivity, and from the viewpoint of fluidity. More preferably, it is 65 volume% to 85 volume%.

In addition, let the content rate (volume%) of the 2nd filler in this specification be the value calculated | required by following Formula.

Content of second filler (volume%) = (Bw / Bd) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd) + (Ew / Ed))) × 100

Here, each variable is as follows.
Aw: Mass composition ratio (% by mass) of the first filler
Bw: mass composition ratio (mass%) of the second filler
Cw: mass composition ratio of thermosetting resin (mass%)
Dw: Curing agent mass composition cost (mass%)
Ew: Mass composition ratio (% by mass) of other optional components (excluding organic solvents)
Ad: Specific gravity of the first filler Bd: Specific gravity of the second filler Cd: Specific gravity of the thermosetting resin Dd: Specific gravity of the curing agent Ed: Specific gravity of other optional components (excluding organic solvents)

The second filler may have a single peak or a plurality of peaks when a particle size distribution curve having a particle diameter on the horizontal axis and a frequency on the vertical axis is drawn. Good. By using the second filler whose particle size distribution curve has a plurality of peaks, the filling property of the second filler is improved, and the thermal conductivity as the cured resin composition is improved.

When the second filler has a single peak when a particle size distribution curve is drawn, the average particle diameter (D50) of the second filler is 1 μm to 80 μm from the viewpoint of thermal conductivity. It is preferably 1 μm to 50 μm. Moreover, the 2nd filler which a particle size distribution curve has a some peak can be comprised combining 2 or more types of 2nd fillers which have a different average particle diameter (D50), for example.

Regarding the combination of the second filler, for example, when two types of filler groups having different average particle diameters are combined, the filler (A) having an average particle diameter (D50) of 10 μm or more and 100 μm or less, and the average particle It is a mixed filler with a filler (B) whose diameter (D50) is ½ or less of the filler (A) and is 1 μm or more and less than 10 μm, and the filler (A) is 60 with respect to the total volume of the second filler. It is preferable that the filler is filled at a ratio of volume% to 90 volume%, and the filler (B) is 10 volume% to 40 volume% (however, the total volume% of the fillers (A) and (B) is 100 volume%). .

Further, when three kinds of fillers having different average particle diameters are combined, a filler (A ′) having an average particle diameter (D50) of 10 μm or more and 100 μm or less and an average particle diameter (D50) of the filler (A ′). A filler (B ′) that is ½ or less of 5 μm or more and less than 10 μm, a filler (C ′) whose average particle diameter (D50) is ½ or less of the filler (B ′) and is 1 μm or more and less than 5 μm; The filler (A ′) is 30% by volume to 89% by volume, the filler (B ′) is 10% by volume to 40% by volume, and the filler (C ′ ) Is preferably 1% by volume to 30% by volume (provided that the total volume% of fillers (A ′), (B ′), and (C ′) is 100% by volume).

The average particle diameter (D50) of the fillers (A) and (A ′) is a cured resin composition in a target resin sheet or laminate when the resin composition is applied to a resin sheet or laminate described later. In the case of applying the resin composition to the prepreg described later, it is preferable to appropriately select the layer thickness and the fineness of the fiber base material according to the target. .

When there is no other restriction, the average particle diameter of the fillers (A) and (A ′) is preferably as large as possible from the viewpoint of thermal conductivity, but the film thickness is insulated from the viewpoint of thermal resistance. It is preferable to make it as thin as possible within the range allowed by the properties. Therefore, the average particle diameter of the fillers (A) and (A ′) is preferably 10 μm to 100 μm, more preferably 10 μm to 80 μm from the viewpoint of filler filling property, thermal resistance, and thermal conductivity. More preferably, it is ˜50 μm.

The fillers (A) and (A ′) are preferably boron nitride or aluminum nitride, but the fillers (B) and (B ′) and the filler (C ′) need not necessarily be boron nitride or aluminum nitride. There is no. For example, alumina may be used.

As described above, when the second filler is constituted by combining filler groups having different average particle diameters (D50), the average particle diameter (D50) is 1 μm to 100 μm in the entire second filler.

The resin composition may further include a third filler having an average particle diameter (D50) outside the range of 1 nm to 500 nm and 1 μm to 100 μm as necessary, and having thermal conductivity. Even when a third filler having an average particle size (D50) outside the range of 1 nm to 500 nm and 1 μm to 100 μm is used in combination, the second filler having an average particle size (D50) of 1 μm to 100 μm is a resin composition. It is preferably contained at 55 volume% to 85 volume% in the total volume of the product.

The average particle diameter (D50) of the third filler is preferably more than 500 nm and less than 1 μm, and more preferably 500 nm or more and 800 nm or less. Moreover, the content rate of the 3rd filler in the case where the said resin composition contains a 3rd filler is not restrict | limited in particular. For example, the total volume of the resin composition is preferably 1% by volume to 40% by volume, and more preferably 1% by volume to 20% by volume.
In addition, the preferable aspect of the heat conductivity of a 3rd filler is the same as that of said 2nd filler.

The ratio of the average particle diameter (D50) of the second filler to the average particle diameter (D50) of the first filler contained in the resin composition (second filler / first filler) is not particularly limited. From the viewpoint of thermal conductivity and fluidity, it is preferably 10 to 500, more preferably 30 to 300. When the particle size distribution curve of the second filler has a plurality of peaks, the ratio of the particle diameter corresponding to the peak having the maximum particle diameter to the average particle diameter (D50) of the first filler is 10 to 500. Preferably, it is preferably 30 to 300.

The ratio (second filler / first filler) of the second filler content (volume%) to the first filler content (volume%) contained in the resin composition is not particularly limited. From the viewpoint of thermal conductivity and fluidity, it is preferably 5 to 500, more preferably 5 to 350.

(Thermosetting resin)
The resin composition contains at least one thermosetting resin having a mesogenic group in the molecule.

Here, the mesogenic group refers to a functional group that facilitates the expression of crystallinity and liquid crystallinity by the action of intermolecular interaction. Specific examples include a biphenyl group, a phenylbenzoate group, an azobenzene group, a stilbene group, and derivatives thereof.

The thermosetting resin in the present invention is not particularly limited as long as it is a compound having at least one mesogenic group and at least two thermosetting functional groups in the molecule. Specific examples include epoxy resins, polyimide resins, polyamideimide resins, triazine resins, phenol resins, melamine resins, polyester resins, cyanate ester resins, and modified resins of these resins. These resins may be used alone or in combination of two or more.

The thermosetting resin is preferably at least one resin selected from an epoxy resin, a phenol resin, and a triazine resin from the viewpoint of heat resistance, and more preferably an epoxy resin from the viewpoint of adhesiveness. The said epoxy resin may be used individually by 1 type, or may use 2 or more types together.

For the specific content of the epoxy resin having a mesogenic group in the molecule (hereinafter also referred to as “mesogen-containing epoxy resin”), reference can be made to, for example, the description of Japanese Patent No. 4118691.

In addition, whether the resin has an anisotropic structure described in Japanese Patent No. 4118691 in the semi-cured body and the cured body of the resin composition depends on the X-ray diffraction of the semi-cured resin composition and the cured resin composition. It can be determined by performing (for example, Rigaku X-ray analyzer). When a CuK _α 1 wire is used and measurement is performed in the range of tube voltage 40 kV, tube current 20 mA, 2θ = 2 ° to 30 °, the resin has an anisotropic structure described in Japanese Patent No. 4118691. In the case of a semi-cured resin composition and a cured resin composition, a peak appears in the range of 2θ = 2 ° to 10 °. In addition, since the peak of the thermally conductive filler made of the highly thermally conductive ceramic appears after 2θ = 20 °, it can be clearly distinguished from the peak of the resin.
Hereinafter, although the specific example of a mesogen containing epoxy resin is shown, the thermosetting resin in this invention is not limited to these.

Examples of the mesogen-containing epoxy resin include an epoxy resin represented by the following general formula (II) (described in Japanese Patent No. 4118691), an epoxy resin represented by the following general formula (III) (Japanese Patent No. 4619770, JP 2008) No. 13759), an epoxy resin represented by the following general formula (IV) (described in JP-A-2011-74366), an epoxy resin represented by the following general formula (V) (JP-A 2010-241797) And an epoxy resin represented by the following chemical formula (VI) (described in JP-A-2011-98952), and the like.

In the general formula (II), n is 4, 6 or 8.

In general formula (III), Ar ¹ , Ar ² , and Ar ³ are the same or different and each represents any divalent group represented by any of the following general formulas, and m represents an integer of 1 to 9 Represent. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Q ¹ and Q ² are the same or different and each represents a linear alkylene group having 1 to 9 carbon atoms, and the methylene group constituting the linear alkylene group is substituted with an alkylene group having 1 to 18 carbon atoms In addition, —O— or —N (R ⁷ ) — may be inserted between the methylene groups. Here, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

Here, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a is an integer of 1 to 8, b, e, and g are integers of 1 to 6, and c is an integer of 1 to 7. , D and h each represents an integer of 1 to 4, and f represents an integer of 1 to 5, respectively. In the above divalent group, when there are a plurality of Rs, all Rs may represent the same group or different groups.

In general formula (IV), R ¹ to R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In general formula (V), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a carbon number Represents an alkoxy group having 1 to 3; R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; R ⁴ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or R 1 represents an alkoxy group having 1 to 3 carbon atoms, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R ⁶ represents a hydrogen atom, an alkyl having 1 to 3 carbon atoms Represents a group or an alkoxy group having 1 to 3 carbon atoms, R ⁷ represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, and R ⁸ represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms. Represents.

Moreover, YL6121H (made by Mitsubishi Chemical Corporation) etc. are mentioned as a commercial item.

The mesogen-containing epoxy resin is preferably an epoxy resin having a structure in which three or more six-membered ring groups are connected in a straight chain in a mesogen group. Such a resin can easily form a higher-order structure, and higher thermal conductivity can be obtained. The number of linearly linked 6-membered cyclic groups contained in the mesogenic group is preferably 3 or more, but more preferably 3 or 4 from the viewpoint of moldability.

The 6-membered cyclic group connected in a straight chain contained in the mesogenic group is a cyclohexane, even if it is a 6-membered cyclic group derived from an aromatic ring represented by acenes such as benzene, pyridine, toluene, or naphthalene. , Cyclohexene, piperidine and other aliphatic rings derived from an aliphatic ring. Among them, at least one is preferably a 6-membered ring group derived from an aromatic ring, and one of the 6-membered ring groups connected in a straight chain contained in the mesogen group is an aliphatic ring, and the remaining More preferably, the rings are all aromatic rings.

Among the aforementioned mesogen-containing epoxy resins, the epoxy resins having a structure in which three or more 6-membered rings are linearly linked in the mesogenic group correspond to the above general formulas (II) to (VI).
Among them, the epoxy resins represented by the following general formulas (VII), (VIII), (IX), and (X) are excellent in fluidity and adhesiveness in addition to thermal conductivity. It can be preferably applied.

(1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene described in Japanese Patent No. 4619770)

(1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) benzene described in Japanese Patent No. 4619770)

(4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) benzoate described in JP 2011-74366 A)

(4- {4- (2,3-epoxypropoxy) phenyl} cyclohexyl 4- (2,3-epoxypropoxy) -3-methyl) benzoate described in JP 2011-74366 A)

The thermosetting resin may be a monomer or a prepolymer obtained by partially reacting the monomer with a curing agent or the like. Resins having a mesogenic group in the molecule are generally easy to crystallize and often have low solubility in a solvent. However, crystallization can be suppressed by partial polymerization, so that moldability may be improved.

The thermosetting resin is preferably contained in an amount of 10 to 40% by volume of the total volume of the total solid content of the resin composition from the viewpoints of moldability, adhesiveness, and thermal conductivity, and 15 volume. More preferably, it is contained in an amount of from 35% to 35% by volume, and more preferably from 15% to 30% by volume.
In addition, when the said resin composition contains the below-mentioned hardening | curing agent and hardening accelerator, the content rate of these hardening | curing agents and hardening accelerator shall be included in the content rate of a thermosetting resin here.

The ratio (thermosetting resin / first filler) of the thermosetting resin content (volume%) to the first filler content (volume%) contained in the resin composition is not particularly limited. From the viewpoint of thermal conductivity and fluidity, it is preferably 1 to 200, more preferably 2.5 to 150.

(Curing agent)
The resin composition preferably includes at least one curing agent. The curing agent is not particularly limited as long as the thermosetting resin can be thermoset. Examples of the curing agent when the thermosetting resin is an epoxy resin include polyaddition curing agents such as acid anhydride curing agents, amine curing agents, phenol curing agents, and mercaptan curing agents, and imidazole. And the like, and the like.
Among these, from the viewpoint of heat resistance, it is preferable to use at least one selected from amine-based curing agents and phenol-based curing agents, and from the viewpoint of storage stability, it is preferable to use at least one phenol-based curing agent. More preferred.

As the amine curing agent, those usually used can be used without particular limitation, and those commercially available may be used. Among these, a polyfunctional curing agent having two or more functional groups is preferable from the viewpoint of curability, and a polyfunctional curing agent having a rigid skeleton is more preferable from the viewpoint of thermal conductivity.

Examples of bifunctional amine curing agents include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino-3,3′-dimethoxybiphenyl 4,4′-diaminophenylbenzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 1,8-diaminonaphthalene and the like.
Among these, from the viewpoint of thermal conductivity, at least one selected from 4,4′-diaminodiphenylmethane and 1,5-diaminonaphthalene is preferable, and 1,5-diaminonaphthalene is more preferable.

As the phenolic curing agent, those usually used can be used without particular limitation, and commercially available low molecular phenolic compounds and phenol resins obtained by novolacizing them can be used.

Examples of low molecular weight phenol compounds include monofunctional compounds such as phenol, o-cresol, m-cresol, and p-cresol, bifunctional compounds such as catechol, resorcinol, and hydroquinone, and 1,2,3-triol. Trifunctional compounds such as hydroxybenzene, 1,2,4-trihydroxybenzene, 1,3,5-trihydroxybenzene and the like can be used. In addition, a phenol novolac resin obtained by connecting these low molecular phenol compounds with a methylene chain to form a novolak can also be used as a curing agent.

The phenolic curing agent is preferably a bifunctional phenolic compound such as catechol, resorcinol, and hydroquinone, or a phenol novolac resin in which these are linked by a methylene chain, and from the viewpoint of heat resistance. Therefore, it is more preferable to use a phenol novolac resin in which these low-molecular bifunctional phenolic compounds are linked by a methylene chain.

Specific examples of phenol novolak resins include cresol novolak resins, catechol novolak resins, resorcinol novolak resins, hydroquinone novolak resins, and the like, which are resins obtained by novolacizing one phenol compound, catechol resorcinol novolak resins, resorcinol hydroquinone novolak resins, and the like. A resin in which two or more phenol compounds are novolakized can be exemplified.

Among these, the phenol novolak resin is preferably a novolak resin containing a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (I-1) and (I-2).

In the general formulas (I-1) and (I-2), each R ¹ independently represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, and aralkyl group represented by R ¹ may further have a substituent, if possible. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroxyl group.
m independently represents an integer of 0 to 2, and when m is 2, two R ^{1 s} may be the same or different. In the present invention, each m is preferably independently 0 or 1, more preferably 0.
Each n independently represents an integer of 1 to 7.

In the general formulas (I-1) and (I-2), R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, and aralkyl group represented by R ² and R ³ may further have a substituent if possible. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroxyl group.

R ² and R ³ in the present invention are preferably a hydrogen atom, an alkyl group, or an aryl group from the viewpoints of storage stability and thermal conductivity, and are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a carbon atom. An aryl group of 6 to 12 is preferable, and a hydrogen atom is more preferable.
Furthermore, from the viewpoint of heat resistance, at least one of R ² and R ³ is preferably an aryl group, more preferably an aryl group having 6 to 12 carbon atoms.
The aryl group may include a hetero atom in the aromatic group, and is preferably a heteroaryl group in which the total number of hetero atoms and carbon is 6 to 12.

The curing agent according to the present invention may contain one type of compound having the structural unit represented by the general formula (I-1) or (I-2) alone, or may contain two or more types. There may be. Preferably, it includes at least a compound having a structural unit derived from resorcinol represented by the general formula (I-1).

The compound having the structural unit represented by the general formula (I-1) may further include at least one partial structure derived from a phenol compound other than resorcinol. Examples of the phenol compound other than resorcinol in the general formula (I-1) include phenol, cresol, catechol, hydroquinone and the like. In this invention, the partial structure derived from these may be included individually by 1 type or in combination of 2 or more types.
Similarly, the compound having a structural unit derived from catechol represented by the general formula (I-2) may contain at least one partial structure derived from a phenol compound other than catechol.

Here, the partial structure derived from the phenol compound means a monovalent or divalent group constituted by removing one or two hydrogen atoms from the benzene ring portion of the phenol compound. The position where the hydrogen atom is removed is not particularly limited.

In the present invention, the partial structure derived from a phenol compound other than resorcinol includes phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxybenzene, from the viewpoint of thermal conductivity, adhesiveness, and storage stability. It is preferably a partial structure derived from at least one selected from 1,2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene, and a portion derived from at least one selected from catechol and hydroquinone A structure is more preferable.

In the compound having the structural unit represented by the general formula (I-1), the content ratio of the partial structure derived from resorcinol is not particularly limited. From the viewpoint of elastic modulus, the content ratio of the partial structure derived from resorcinol to the total mass of the compound having the structural unit represented by formula (I-1) is preferably 55% by mass or more. Furthermore, from the viewpoint of Tg and linear expansion coefficient, it is more preferably 60% by mass or more, further preferably 80% by mass or more, and further preferably 90% by mass or more from the viewpoint of thermal conductivity. .

Furthermore, the phenol novolak resin of the present invention is a novolak resin containing a compound having a structure represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4). preferable.

Further, the phenol novolak resin is more preferably a novolak resin containing a compound having a structure represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4): .

In the above general formulas (II-1) to (II-2), m and n are each independently a positive number, and indicate the number of repetitions of each repeating unit. Ar represents a group represented by any one of the following general formulas (II-a) and (II-b).

In the general formulas (II-a) and (II-b), R ¹¹ and R ¹⁴ each independently represents a hydrogen atom or a hydroxyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The curing agent having a partial structure represented by at least one of the above general formulas (II-1) to (II-4) is produced as a by-product by a production method described later in which a divalent phenol compound is novolakized. It is possible.

The partial structures represented by the general formulas (II-1) to (II-4) may be included as the main chain skeleton of the curing agent or may be included as a part of the side chain. Further, each repeating unit constituting the partial structure represented by any one of the general formulas (II-1) to (II-4) may be included randomly or regularly. It may be included or may be included in a block shape.

In the general formulas (II-1) to (II-4), the hydroxyl substitution position is not particularly limited as long as it is on the aromatic ring.

In each of the above general formulas (II-1) to (II-4), a plurality of Ar may all be the same atomic group or may contain two or more kinds of atomic groups. Ar represents a group represented by any one of the general formulas (II-a) and (II-b).

R ¹¹ and R ¹⁴ in the general formulas (II-a) and (II-b) are each independently a hydrogen atom or a hydroxyl group, but are preferably a hydroxyl group from the viewpoint of thermal conductivity. Further, the substitution positions of R ¹¹ and R ¹⁴ are not particularly limited.

In the general formulas (II-a) and (II-b), R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms in R ¹² and R ¹³ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl Group, and octyl group. In addition, the substitution positions of R ¹² and R ^{13 in} the general formulas (II-a) and (II-b) are not particularly limited.

Ar in the above general formulas (II-a) and (II-b) is a group derived from dihydroxybenzene (from the above general formula (II-a), from the viewpoint of achieving the effects of the present invention, particularly excellent thermal conductivity. And a group derived from dihydroxynaphthalene (a group in which R ¹⁴ is a hydroxyl group in the above general formula II-b), and at least R ¹¹ is a hydroxyl group and R ¹² and R ¹³ are hydrogen atoms) One type is preferable.

Here, the “group derived from dihydroxybenzene” means a divalent group formed by removing two hydrogen atoms from the aromatic ring portion of dihydroxybenzene, and the position at which the hydrogen atom is removed is not particularly limited. In addition, “group derived from dihydroxynaphthalene” has the same meaning.

Further, from the viewpoint of productivity and fluidity of the epoxy resin composition, Ar is more preferably a group derived from dihydroxybenzene, and a group derived from 1,2-dihydroxybenzene (catechol) and 1, More preferably, it is at least one selected from the group consisting of groups derived from 3-dihydroxybenzene (resorcinol). Furthermore, it is preferable that at least a group derived from resorcinol is included as Ar from the viewpoint of particularly improving thermal conductivity.
Further, from the viewpoint of particularly improving the thermal conductivity, the structural unit represented by the repeating number n preferably contains a group derived from resorcinol.

The content of the structural unit containing a group derived from resorcinol is 55% by mass or more in the total mass of the compound having a partial structure represented by at least one of general formulas (II-1) to (II-4) It is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

In the general formulas (II-1) to (II-4), m and n are preferably m / n = 20/1 to 1/5 from the viewpoint of fluidity, and 20/1 to 5/1. It is more preferable that the ratio is 20/1 to 10/1. Further, (m + n) is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less from the viewpoint of fluidity.
In addition, the lower limit of (m + n) is not particularly limited.

Phenol novolac resins having a partial structure represented by at least one of the general formulas (II-1) to (II-4) are particularly those in which Ar is substituted or unsubstituted dihydroxybenzene and substituted or unsubstituted dihydroxynaphthalene. In the case of at least one of them, compared with a resin or the like obtained by simply novolacizing them, the synthesis is easy and a curing agent having a low softening point tends to be obtained. Therefore, there are advantages such as easy manufacture and handling of a resin composition containing such a resin.
The phenol novolak resin having a partial structure represented by any one of the above general formulas (II-1) to (II-4) is obtained as a fragment component thereof by the field desorption ionization mass spectrometry (FD-MS). The structure can be easily identified.

In the present invention, the molecular weight of the phenol novolac resin having a partial structure represented by any one of the general formulas (II-1) to (II-4) is not particularly limited. From the viewpoint of fluidity, the number average molecular weight (Mn) is preferably 2000 or less, more preferably 1500 or less, and further preferably 350 or more and 1500 or less. Further, the weight average molecular weight (Mw) is preferably 2000 or less, more preferably 1500 or less, and further preferably 400 or more and 1500 or less.
These Mn and Mw are measured by a normal method using GPC.

In the present invention, the hydroxyl equivalent of the phenol novolac resin having a partial structure represented by any one of the general formulas (II-1) to (II-4) is not particularly limited. From the viewpoint of the crosslinking density involved in heat resistance, the hydroxyl group equivalent is preferably 50 to 150 in average, more preferably 50 to 120, and even more preferably 55 to 120.

In the present invention, the phenol novolac resin may contain a monomer that is a phenol compound constituting the phenol novolac resin. There is no particular limitation on the content ratio of the monomer that is a phenol compound constituting the phenol novolac resin (hereinafter also referred to as “monomer content ratio”). From the viewpoint of thermal conductivity, heat resistance, and moldability, it is preferably 5% by mass to 80% by mass, more preferably 15% by mass to 60% by mass, and 20% by mass to 50% by mass. More preferably.

When the monomer content is 80% by mass or less, the amount of monomers that do not contribute to crosslinking during the curing reaction is reduced and the number of crosslinked high molecular weight substances is increased, so that a higher-order higher-order structure is formed and heat conduction is increased. Improves. Moreover, since it is easy to flow at the time of shaping | molding because it is 5 mass% or more, adhesiveness with a filler improves more and more excellent thermal conductivity and heat resistance can be achieved.

The content of the curing agent in the resin composition is not particularly limited. For example, when the curing agent is an amine curing agent, the ratio of the active hydrogen equivalent of the amine curing agent (amine equivalent) to the epoxy equivalent of the mesogen-containing epoxy resin (amine equivalent / epoxy equivalent) is 0.5 to 2 is preferable, and 0.8 to 1.2 is more preferable. Further, when the curing agent is a phenolic curing agent, the ratio of the active hydrogen equivalent of the phenolic hydroxyl group (phenolic hydroxyl group equivalent) to the epoxy equivalent of the mesogen-containing epoxy resin (phenolic hydroxyl group equivalent / epoxy equivalent) is 0. 0.5 to 2 is preferable, and 0.8 to 1.2 is more preferable.

Also, when using a phenolic curing agent, a curing accelerator may be used in combination as necessary. By using a curing accelerator in combination, it can be further sufficiently cured. Although the kind and compounding quantity of a hardening accelerator are not specifically limited, An appropriate thing can be selected from viewpoints, such as reaction rate, reaction temperature, and storage property. Specific examples of the curing accelerator include imidazole compounds, organic phosphorus compounds, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more.

(Silane coupling agent)
The resin composition preferably further includes at least one silane coupling agent. As an effect of adding a silane coupling agent, it plays a role of forming a covalent bond between the surface of the first filler or the second filler and the thermosetting resin surrounding the surface (equivalent to a binder agent), and heat This also contributes to the improvement of insulation reliability by preventing the penetration of moisture.

The type of the silane coupling agent is not particularly limited, and a commercially available product may be used. In consideration of reducing the thermosetting resin (preferably an epoxy resin), compatibility with a curing agent contained as necessary, and reducing heat conduction defects at the interface between the resin and the filler, It is preferable to use a silane coupling agent having an epoxy group, amino group, mercapto group, ureido group, or hydroxyl group at the terminal.

Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxy Examples thereof include silane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptotriethoxysilane, and 3-ureidopropyltriethoxysilane. Further, silane coupling agent oligomers (manufactured by Hitachi Chemical Coated Sand Co., Ltd.) represented by SC-6000KS2 can also be mentioned.
These silane coupling agents may be used alone or in combination of two or more.

The resin composition may further contain at least one organic solvent. By including an organic solvent, it can be adapted to various molding processes. As the organic solvent, a commonly used organic solvent can be used. Specific examples include alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents, and the like. For example, methyl isobutyl ketone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, methyl ethyl ketone and the like can be used. These may be used alone or as a mixed solvent using two or more kinds in combination.

The resin composition in the present invention can contain other components as necessary in addition to the above components. For example, a dispersing agent, a plasticizer, etc. are mentioned. As the dispersant, for example, Ajinomoto Finetech Co., Ltd. Ajisper series, Enomoto Kasei Co., Ltd. HIPLAAD series, Kao Corporation homogenol series, and the like can be mentioned. Two or more kinds of these dispersants can be used in combination.

<Semi-cured resin composition>
The semi-cured resin composition of the present invention is derived from the resin composition, and is obtained by semi-curing the resin composition. For example, when the semi-cured resin composition is molded into a sheet, the handleability is improved as compared with a resin sheet made of a resin composition that is not semi-cured.

Here, the semi-cured resin composition means that the viscosity of the semi-cured resin composition is 10 ⁴ Pa · s to 10 ⁵ Pa · s at room temperature (25 to 30 ° C.), whereas the viscosity is 100 ° C. Then, it has a feature that it is reduced to 10 ² Pa · s to 10 ³ Pa · s. Moreover, the cured resin composition after curing described later is not melted by heating. The viscosity is measured by dynamic viscoelasticity measurement (DMA) (for example, ARES-2KSTD manufactured by TA Instruments). The measurement conditions are a frequency of 1 Hz, a load of 40 g, a temperature increase rate of 3 ° C./min, and a shear test.

Examples of the semi-curing treatment include a method of heating the resin composition at a temperature of 100 ° C. to 200 ° C. for 1 minute to 30 minutes.

<Curing resin composition>
The cured resin composition of the present invention is derived from the resin composition, and is obtained by curing the resin composition. The cured resin composition is excellent in thermal conductivity and insulation, which can be considered, for example, because a curable resin having a mesogenic group in the molecule contained in the resin composition forms a higher order structure. .

The cured resin composition can be produced by curing the uncured resin composition or the semi-cured resin composition. The method for the curing treatment can be appropriately selected according to the composition of the resin composition, the purpose of the cured resin composition, and the like, but is preferably a heating / pressurizing treatment.
For example, an uncured resin composition or the semi-cured resin composition is heated at 100 ° C. to 250 ° C. for 1 hour to 10 hours, preferably at 130 ° C. to 230 ° C. for 1 hour to 8 hours. Is obtained.

<Resin sheet>
The resin sheet of the present invention is formed by molding the resin composition into a sheet shape. The said resin sheet can be manufactured by apply | coating the said resin composition on a release film, for example, and removing the solvent contained as needed. By forming the resin sheet from the resin composition, the resin sheet is excellent in thermal conductivity, fluidity, and flexibility.

The thickness of the resin sheet is not particularly limited and can be appropriately selected depending on the purpose. For example, the thickness of the resin sheet can be 50 μm to 500 μm, and is preferably 80 μm to 300 μm from the viewpoints of thermal conductivity, electrical insulation, and flexibility.

The resin sheet is, for example, a varnish-like resin composition (hereinafter referred to as “resin varnish”) prepared by adding an organic solvent such as methyl ethyl ketone or cyclohexanone to the resin composition on a release film such as a PET film. Can be produced by removing at least a part of the organic solvent from the coating layer and drying.

Application of the resin varnish can be performed by a known method. Specific examples include methods such as comma coating, die coating, lip coating, and gravure coating. As a coating method for forming the resin composition layer with a predetermined thickness, a comma coating method in which an object to be coated is passed between gaps, a die coating method in which a resin varnish whose flow rate is adjusted from a nozzle, or the like is applied. For example, when the thickness of the coating layer (resin composition layer) before drying is 50 μm to 500 μm, it is preferable to use a comma coating method.

The drying method is not particularly limited as long as at least a part of the organic solvent contained in the resin varnish can be removed, and can be appropriately selected from commonly used drying methods according to the organic solvent contained in the resin varnish. In general, a heat treatment method at about 80 ° C. to 150 ° C. can be mentioned.

Since the resin composition layer of the resin sheet has almost no curing reaction, it has flexibility, but it has poor flexibility as a sheet, and in the state in which the PET film as a support is removed, the sheet is self-supporting. It is scarce and difficult to handle.

The resin sheet is preferably a semi-cured resin composition obtained by semi-curing a resin composition constituting the resin sheet. That is, the resin sheet is preferably a B stage sheet that is further heat-treated until it is in a semi-cured state (B stage state). Since the resin sheet is composed of a semi-cured resin composition obtained by semi-curing the resin composition, it has excellent thermal conductivity and electrical insulation, and is flexible and usable as a B-stage sheet. Excellent.

Here, the viscosity of the B stage sheet is 10 ⁴ Pa · s to 10 ⁵ Pa · s at room temperature (25 to 30 ° C.), whereas it is 10 ² Pa · s to 10 ^{3 at} 100 ° C. It has a feature of lowering to Pa · s. Moreover, the cured resin composition after curing described later is not melted by heating. The viscosity is measured by DMA (frequency 1 Hz, load 40 g: temperature rising rate 3 ° C./min).

The conditions for heat-treating the resin sheet are not particularly limited as long as the resin composition layer can be in a B-stage state, and can be appropriately selected according to the configuration of the resin composition. For the heat treatment, a heat treatment method selected from hot vacuum press, hot roll laminating and the like is preferable for the purpose of eliminating voids in the resin layer generated during coating. Thereby, a flat B stage sheet | seat can be manufactured efficiently.

Specifically, for example, the resin composition is heated and pressurized under reduced pressure (for example, 1 kPa) at a temperature of 100 ° C. to 200 ° C. for 1 second to 90 seconds with a press pressure of 1 MPa to 20 MPa. It can be semi-cured to the stage state.

In addition, when semi-curing to the B stage state, the cured resin composition produced by the method described later is made to have higher thermal conductivity by laminating two coated / dried resin sheets and performing the above heating / pressurizing treatment. Indicates the rate. At this time, it is necessary to bond the application surfaces (the surfaces on the upper side during application, that is, the surfaces opposite to the surfaces in contact with the PET film), whereby both sides of the resin sheet become flatter.

The thickness of the B stage sheet can be appropriately selected according to the purpose, and can be, for example, 50 μm to 500 μm. From the viewpoint of thermal conductivity, electrical insulation, and flexibility, the thickness is 80 μm to 300 μm. Preferably there is. It can also be produced by hot pressing while laminating two or more resin sheets.

The solvent remaining rate in the B-stage sheet is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of concern about bubble formation when outgas is generated during curing. More preferably, it is 0.8 mass% or less.

The solvent residual rate is determined from the change in mass before and after drying when a B-stage sheet is cut into a 40 mm square and dried in a thermostat preheated to 190 ° C. for 2 hours.

The B stage sheet has excellent fluidity. Specifically, the flow amount in the B stage sheet is preferably 130% to 210%, and more preferably 150% to 200%. This flow amount is an indicator of melt fluidity during thermocompression bonding. When the flow amount is 130% or more, sufficient embeddability can be obtained, and when it is 210% or less, generation of burrs due to excessive flow can be suppressed.

The amount of flow is the area of the B stage sheet before and after pressing a sample obtained by punching a 10 mm square B stage sheet having a thickness of 200 μm for 1 minute under conditions of atmospheric pressure, temperature of 180 ° C. and pressing pressure of 15 MPa. Calculated as the rate of change. The area change rate is obtained from the change rate of the area (number of pixels) after taking an external projection image of the sample with a scanner of 300 DPI or more, binarizing with image analysis software (AdobeＡPhotoshop).

Flow amount (%) = (area of B stage sheet after pressing) / (area of B stage sheet before pressing)

The resin sheet may be a cured resin composition obtained by curing the resin composition. A resin sheet made of the cured resin composition can be produced by curing an uncured resin sheet or B-stage sheet. The method for the curing treatment can be appropriately selected according to the composition of the resin composition, the purpose of the cured resin composition, and the like, but is preferably a heating / pressurizing treatment.
For example, an uncured resin sheet or B stage sheet is heated at 100 ° C. to 250 ° C. for 1 hour to 10 hours, preferably 130 ° C. to 230 ° C. for 1 hour to 8 hours. Is obtained. The heating is preferably performed while applying a pressure of 1 MPa to 20 MPa.

As an example of a method for producing a resin sheet comprising a cured resin composition having excellent thermal conductivity, first, a roughened surface of a copper foil (thickness 80 to 120 μm) having a roughened surface on one side of a B stage sheet. The B stage sheet and the copper foil are bonded together by heating and pressing at a pressure of 1 MPa to 20 MPa at a temperature of 130 ° C. to 230 ° C. for 3 minutes to 10 minutes. Subsequently, there is a method of heating at 130 ° C. to 230 ° C. for 1 to 8 hours and removing the copper foil portion of the obtained resin sheet with copper foil by etching treatment to obtain a resin sheet made of the cured resin composition. .

<Prepreg>
The prepreg of the present invention comprises a fiber base material and the resin composition impregnated in the fiber base material. With such a configuration, a prepreg excellent in thermal conductivity and insulation is obtained. Moreover, since the thixotropy improves the resin composition containing the said alumina filler, it can suppress sedimentation of the 2nd filler in the coating process and impregnation process mentioned later. Therefore, the occurrence of the density distribution of the second filler in the thickness direction of the prepreg can be suppressed, and as a result, a prepreg excellent in thermal conductivity and insulation can be obtained.

The fiber base material constituting the prepreg is not particularly limited as long as it is usually used when producing a metal foil-clad laminate or a multilayer printed wiring board, and a fiber base material such as a woven fabric or a nonwoven fabric is usually used. .

The opening of the fiber base material is not particularly limited. From the viewpoint of thermal conductivity and insulating properties, the mesh opening is preferably 5 times or more the average particle diameter (D50) of the second filler. Further, when the particle size distribution curve of the second filler has a plurality of peaks, the opening is more preferably 5 times or more the particle diameter corresponding to the peak having the largest particle diameter.

The material of the fiber base material is not particularly limited. Specifically, inorganic fibers such as glass, alumina, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyether ether ketone, polyether imide, polyether sulfone, carbon , Organic fibers such as cellulose, and mixed papers thereof. Among these, glass fiber woven fabric is preferably used. Thereby, for example, when a printed wiring board is configured using a prepreg, a printed wiring board that is flexible and can be arbitrarily bent can be obtained. Furthermore, it becomes possible to reduce the dimensional change of the printed wiring board accompanying the temperature change or moisture absorption in the manufacturing process.

The thickness of the fiber base material is not particularly limited. From the viewpoint of imparting better flexibility, the thickness is more preferably 30 μm or less, and from the viewpoint of impregnation, it is preferably 15 μm or less. Although the minimum of the thickness of a fiber base material is not restrict | limited in particular, Usually, it is about 5 micrometers.

The impregnation amount (content ratio) of the resin composition in the prepreg is preferably 50% by mass to 99.9% by mass with respect to the total mass of the fiber base material and the resin composition.

The prepreg is produced by impregnating a fiber base material with the resin composition prepared in the same manner as described above, and removing at least a part of the organic solvent by a heat treatment at 80 ° C. to 150 ° C. Can do.

There is no particular limitation on the method for impregnating the fiber base material with the resin composition. For example, the method of apply | coating with a coating machine can be mentioned. In detail, mention is made of a vertical coating method in which the fiber base material is pulled through the resin composition, and a horizontal coating method in which the resin composition is applied on the support film and then impregnated by pressing the fiber base material. Can do. From the viewpoint of suppressing the uneven distribution of the second filler in the fiber base material, the horizontal coating method is preferable.

The prepreg in the present invention may be used after the surface has been smoothed in advance by hot pressing with a press or a roll laminator before being laminated or pasted. The method of the hot press treatment is the same as the method mentioned in the method for producing the B stage sheet. In addition, the processing conditions such as the heating temperature, the degree of pressure reduction, and the pressing pressure in the hot pressurizing process of the prepreg are the same as the conditions mentioned in the heating / pressurizing process of the B stage sheet.

The solvent residual ratio in the prepreg is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and further preferably 0.8% by mass or less.

The solvent residual rate is determined from the mass change before and after drying when the prepreg is cut into 40 mm square and dried in a thermostat preheated to 190 ° C. for 2 hours.

<Laminated plate>
The laminated board in this invention has a to-be-adhered material and the semi-hardened resin composition layer or hardened resin composition layer arrange | positioned on the said to-be-adhered material. The semi-cured resin composition layer and the cured resin composition layer are derived from at least one selected from a resin composition layer composed of the resin composition, the resin sheet, and the prepreg. A layer and a cured resin composition layer. By having a semi-cured resin composition layer or a cured resin composition layer formed from the resin composition, a laminate having excellent thermal conductivity and insulation is obtained.

Examples of the adherend include metal foil and metal plate. The adherend may be attached to only one surface of the semi-cured resin composition layer or the cured resin composition layer, or may be attached to both surfaces.

The metal foil is not particularly limited and can be appropriately selected from commonly used metal foils. Specifically, gold foil, copper foil, aluminum foil, etc. can be mentioned, and copper foil is generally used. The thickness of the metal foil is not particularly limited as long as it is 1 μm to 200 μm, and a suitable thickness can be selected according to the electric power used.

Further, as the metal foil, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy or the like is used as an intermediate layer, and a copper layer of 0.5 μm to 15 μm and a layer of 10 μm to A three-layer composite foil provided with a 150 μm copper layer, or a two-layer composite foil in which aluminum and copper foil are combined can also be used.

The metal plate is preferably made of a metal material having a high thermal conductivity and a large heat capacity. Specific examples include copper, aluminum, iron, and alloys used for lead frames.

The thickness of the metal plate can be appropriately selected according to the application. For example, the material of the metal plate can be selected according to the purpose, such as aluminum when priority is given to weight reduction and workability, and copper when priority is given to heat dissipation.

In the said laminated board, even if it is a form which has 1 layer derived from any one of the said resin composition layer, the said resin sheet, or the said prepreg as a semi-hardened resin composition layer or a cured resin composition layer. Alternatively, a form in which two or more layers are stacked may be used. When it has two or more semi-cured resin composition layers or cured resin composition layers, it has a form having two or more resin composition layers, a form having two or more resin sheets, and two or more prepregs. Any form may be sufficient. Furthermore, you may have in combination any 2 or more of the said resin composition layer, the said resin sheet, and the said prepreg.

The laminated board in the present invention is formed, for example, by coating the resin composition on an adherend to form a resin composition layer, which is heated and pressurized to semi-cur or cure the resin composition layer. It is obtained by making it adhere to an adherend. Alternatively, it is obtained by preparing a laminate of the resin sheet or the prepreg on the adherend and heating and pressurizing it to make the resin sheet or the prepreg semi-cured or cured and to adhere to the adherend. It is done.

The curing method for semi-curing or curing the resin composition layer, the resin sheet, and the prepreg is not particularly limited. For example, heat treatment and pressure treatment are preferable. The heating temperature in the heating and pressure treatment is not particularly limited. Usually, it is in the range of 100 ° C to 250 ° C, preferably in the range of 130 ° C to 230 ° C. Moreover, the pressurization conditions in a heating and pressurizing process are not specifically limited. Usually, it is in the range of 1 MPa to 20 MPa, preferably in the range of 1 MPa to 15 MPa. Moreover, a vacuum press is used suitably for a heating and pressurizing process.

The thickness of the laminate is preferably 500 μm or less, and more preferably 100 μm to 300 μm. When the thickness is 500 μm or less, the flexibility is excellent and the occurrence of cracks during bending is suppressed, and when the thickness is 300 μm or less, the tendency is more visible. Further, when the thickness is 100 μm or more, the workability is excellent.

<Hardened resin with metal foil, metal substrate>
As an example of the said laminated board, the resin cured material with metal foil and metal substrate which can be used for producing the below-mentioned printed wiring board can be mentioned.

The resin cured product with metal foil is constituted by using two metal foils as adherends in the laminate. Specifically, one metal foil, the cured resin composition layer, and the other metal foil are laminated in this order.
Details of the metal foil and the cured resin composition layer constituting the cured resin product with metal foil are as described above.

Moreover, the said metal substrate is comprised using a metal foil and a metal plate as an adherend in the said laminated board. Specifically, the metal substrate is configured by laminating the metal foil, the cured resin composition layer, and the metal plate in this order.
Details of the metal foil and the cured resin composition layer constituting the metal substrate are as described above.

The metal plate is not particularly limited, and can be appropriately selected from commonly used metal plates. Specifically, an aluminum plate, an iron plate, etc. can be mentioned. The thickness of the metal plate is not particularly limited. From the viewpoint of workability, the thickness is preferably 0.5 mm or more and 5 mm or less.

Further, from the viewpoint of improving productivity, the metal plate is preferably cut to a size to be used after being manufactured in a size larger than necessary and mounting an electronic component. Therefore, it is desirable that the metal plate used for the metal substrate is excellent in cutting workability.

When aluminum is used as the metal plate, aluminum or an alloy mainly composed of aluminum can be selected as the material. Many types of aluminum or alloys containing aluminum as a main component are available depending on the chemical composition and heat treatment conditions. Among them, it is preferable to select a type having high workability such as easy cutting and excellent strength.

<Printed wiring board>
The printed wiring board of the present invention is formed by laminating a metal plate, a cured resin composition layer, and a wiring layer in this order. The cured resin composition layer is a cured resin composition layer derived from at least one selected from a resin composition layer composed of the resin composition, the resin sheet, and the prepreg. By having the cured resin composition layer formed from the resin composition, a printed wiring board excellent in thermal conductivity and insulation is obtained.

The printed wiring board can be produced by subjecting at least one metal foil in the resin cured product with metal foil described above or a metal foil on a metal substrate to circuit processing. An ordinary photolithography method can be applied to the circuit processing of the metal foil.

Preferable embodiments of the printed wiring board include, for example, those similar to the printed wiring board described in paragraph No. 0064 of JP2009-214525A and paragraph Nos. 0056 to 0059 of JP2009-275086A. be able to.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

The material used for preparation of the resin composition and its abbreviation are shown below.
(First filler)
HIT-70 [α-alumina, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 150 nm]
AA-04 [α-alumina, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 400 nm]

(Second filler)
HP-40 [Boron nitride, manufactured by Mizushima Alloy Iron Co., Ltd., average particle size: 18 μm]
FAN-f30 [Aluminum nitride, manufactured by Furukawa Denshi Co., Ltd., average particle size: 30 μm]
FAN-f05 [Aluminum nitride, manufactured by Furukawa Denshi Co., Ltd., average particle size: 5 μm]

(Third filler)
ShapalH [Aluminum nitride, manufactured by Tokuyama Corporation, average particle size: 0.6 μm]

(Thermosetting resin)
・ Resin A below (see Japanese Patent No. 4619770)

・ Resin B below (see Japanese Patent No. 4619770)

・ The following resin C (refer to JP 2011-74366 A)

・ The following resin D (refer to JP 2011-74366 A)

(Curing agent)
CRN [catechol resorcinol novolak (preparation ratio: 5/95) resin, manufactured by Hitachi Chemical Co., Ltd., containing 50% cyclohexanone]
<Synthesis method of CRN>
Into a 3 L separable flask equipped with a stirrer, a cooler, and a thermometer, 627 g of resorcinol, 33 g of catechol, 316.2 g of 37% formaldehyde, 15 g of oxalic acid, and 300 g of water were heated to 100 ° C. while heating in an oil bath. The temperature rose. The mixture was refluxed at around 104 ° C., and the reaction was continued at the reflux temperature for 4 hours. Thereafter, the temperature in the flask was raised to 170 ° C. while distilling off water. The reaction was continued for 8 hours while maintaining 170 ° C. After the reaction, concentration was performed under reduced pressure for 20 minutes to remove water and the like in the system, and the target phenol resin CRN was obtained.
Further, when the structure of the obtained CRN was confirmed by FD-MS, the existence of all the partial structures represented by the general formulas (II-1) to (II-4) was confirmed.

Note that, under the above reaction conditions, a compound having a partial structure represented by the general formula (II-1) is formed first, and this is further subjected to a dehydration reaction, whereby general formulas (II-1) to (II-4) It is considered that a compound having a partial structure represented by at least one of them is produced.

The obtained CRN was measured for Mn and Mw as follows.
Mn and Mw were measured using a high performance liquid chromatography L6000 manufactured by Hitachi, Ltd. and a data analyzer C-R4A manufactured by Shimadzu Corporation. G2000HXL and G3000HXL manufactured by Tosoh Corporation were used as analytical GPC columns. The sample concentration was 0.2% by mass, tetrahydrofuran was used as the mobile phase, and the measurement was performed at a flow rate of 1.0 ml / min. A calibration curve was prepared using a polystyrene standard sample, and Mn and Mw were calculated using polystyrene conversion values.

With respect to the obtained CRN, the hydroxyl equivalent was measured as follows.
The hydroxyl equivalent was measured by acetyl chloride-potassium hydroxide titration method. The determination of the titration end point was performed by potentiometric titration instead of the coloring method using an indicator because the solution color was dark. Specifically, the hydroxyl group of the measurement resin is acetylated in a pyridine solution, the excess reagent is decomposed with water, and the resulting acetic acid is titrated with a potassium hydroxide / methanol solution.
The obtained CRN is shown below.

A mixture of compounds having a partial structure represented by at least one of general formulas (II-1) to (II-4), wherein Ar is R ¹¹ = hydroxyl group in general formula (II-a) A group derived from 1,2-dihydroxybenzene (catechol) in which R ¹² = R ¹³ = hydrogen atom and a group derived from 1,3-dihydroxybenzene (resorcinol), and a monomer as a low molecular diluent It was a phenol resin containing a curing agent (hydroxyl equivalent 62, number average molecular weight 422, weight average molecular weight 564) containing 35% of the component (resorcinol).

(Additive)
・ TPP: Triphenylphosphine [curing accelerator]
・ KBM-573: 3-phenylaminopropyltrimethoxysilane [Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.]

(solvent)
CHN: cyclohexanone

(Support)
・ PET film [Fujimori Kogyo Co., Ltd., 75E-0010CTR-4]
・ Copper foil [Furukawa Electric Co., Ltd., thickness: 80 μm, GTS grade]

Example 1
<Preparation of resin composition>
First filler (α-alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 70.29% by mass, thermosetting resin (resin A) 10.22% by mass Curing agent (CRN) 6.30% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 12.56% by mass. An epoxy resin varnish was obtained as a resin composition containing a solvent.

The density of the alumina is 3.97 g / cm ³ , the density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of Resin A and CRN is 1.20 g / cm ³ . It was 0.26 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening | curing agent was computed. Moreover, it was 74 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

<Preparation of B stage sheet>
The epoxy resin varnish produced above was applied on a PET film using an applicator so that the thickness after drying was 200 μm, and then dried at 100 ° C. for 10 minutes. Thereafter, hot pressing (press temperature: 180 ° C., degree of vacuum: 1 kPa, press pressure: 15 MPa, processing time: 60 seconds) is performed by a vacuum press to obtain a B stage sheet as a resin sheet of the semi-cured resin composition. It was.

<Evaluation of flow amount>
After peeling off the PET film of the B stage sheet (thickness: 200 μm) obtained above, it was punched out to 10 mm square, and using a press machine, atmospheric pressure, temperature: 180 ° C., press pressure: 15 MPa, 1 minute Pressurized and crushed. An external projection image of the crushed sample was captured with a scanner of 300 DPI or more, binarized with image analysis software (Adobe Photoshop), and then the flow amount was evaluated from the change rate of the area (number of pixels) before and after crushing.

<Preparation of cured resin with copper foil>
After peeling off the PET film of the B-stage sheet obtained above, it was sandwiched between two copper foils with their mat surfaces facing the B-stage sheet, and vacuum-pressed with a vacuum press (temperature: 180 ° C. Vacuum degree: 1 kPa, press pressure: 15 MPa, treatment time: 8 minutes). Then, it heated at 140 degreeC for 2 hours, 165 degreeC for 2 hours, and also at 190 degreeC for 2 hours under atmospheric pressure conditions, and obtained resin cured material with copper foil.

<Measurement of thermal conductivity>
(Hardened resin sheet)
The copper foil of the resin cured product with copper foil obtained above was removed by etching to obtain a cured resin sheet as a cured resin composition. The obtained cured resin sheet was cut into 10 mm squares and blackened with graphite spray, and then the thermal diffusivity was evaluated using a xenon flash method (LFA447 nanoflash manufactured by NETZSCH). From the product of this value, the density measured by the Archimedes method, and the specific heat measured by DSC (DSC Pyris 1 manufactured by Perkin Elmer), the thermal conductivity of the cured resin sheet was determined.
The results are shown in Table 1.

Moreover, the heat conductivity of the resin part in resin sheet cured | curing material was converted and calculated | required using the following Formula from the heat conductivity of the resin sheet cured | curing material obtained above.
1−ν = [(λmix−λres) / (λres−λfil)] × (λres / λmix) ^x
(However, x = 1 / (1 + χ))
The results are shown in Table 1.

λmix: Thermal conductivity of resin sheet (W / mK)
λres: Thermal conductivity of resin part in resin sheet (W / mK)
λfil: thermal conductivity (W / mK) of the filler portion in the resin sheet (60 when the second filler is boron nitride, 60 when the mixture of boron nitride and alumina, and 130 when aluminum nitride is used)
ν: Volume fraction of filler (% by volume)
χ: Filler shape parameter (3.1 when the second filler is boron nitride, 2.2 when aluminum nitride is used)

(Cured resin without filler)
The mixture of the thermosetting resin, the curing agent, and the curing accelerator used for the preparation of the resin composition was melted and sandwiched between two aluminum plates (thickness: 200 μm), and the pressure was 1 at 140 ° C. under atmospheric pressure conditions. Heating was performed for 1 hour at 165 ° C. for 1 hour and further at 190 ° C. for 1 hour to obtain a resin-cured product without filler with aluminum plate (thickness: about 150 μm).

The thermal diffusivity of the cured resin product obtained by peeling the aluminum plate from the filler-free resin cured product with an aluminum plate was evaluated using a temperature wave thermal analyzer (ai-Phase mobile 1u manufactured by ai-Phase). From this value and the product of the density and specific heat obtained by the above-mentioned method, the thermal conductivity of the resin-free cured resin is obtained, and this is the thermal conductivity of the resin part in the cured resin sheet (cured resin composition). Rate.
The results are shown in Table 1.

<Measurement of breakdown voltage>
The copper foil of the resin cured product with copper foil obtained above was removed by etching to obtain a cured resin sheet as a cured resin composition. The obtained resin sheet cured product was cut out with a dimension of 100 mm square or more and used as a sample. Using a YST-243-100RHO made by YAMAYO SEIKI CO., LTD., Sandwiching it with a cylindrical electrode with a diameter of 25 mm, measuring the dielectric breakdown voltage at a pressure increase rate of 500 V / s at room temperature in the atmosphere, Average and minimum values were determined.
The results are shown in Table 1.

(Example 2)
First filler (α-alumina, mixture of HIT-70: 0.45 vol% and AA-04: 11.76 vol%) 12.21% by mass, second filler (boron nitride, HP-40) 58 .53 mass%, thermosetting resin (resin A) 10.22 mass%, curing agent (CRN) 6.30 mass%, curing accelerator (TPP) 0.11 mass%, silane coupling agent (KBM-573) ) 0.07% by mass and 12.56% by mass of solvent (CHN) were mixed to obtain an epoxy resin varnish as a resin composition containing the solvent.

The density of the alumina is 3.97 g / cm ³ , the density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of Resin A and CRN is 1.20 g / cm ³ . It was 7.5 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening | curing agent was computed. Moreover, it was 65 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

A B stage sheet and a cured resin product with a copper foil were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above.
The results are shown in Table 1.

(Example 3)
First filler (α-alumina, HIT-70) 0.45% by mass, second filler 63.84% by mass (aluminum nitride, FAN-f30: 49.02% by volume and FAN-f05: 14.82% by volume) % Filler), third filler (aluminum nitride, ShapalH) 10.39 mass%, thermosetting resin (resin A) 7.23 mass%, curing agent (CRN) 4.46 mass%, curing accelerator ( TPP) 0.08% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 13.48% by mass were mixed to obtain an epoxy resin varnish as a resin composition containing the solvent. .

The density of the alumina is 3.97 g / cm ³ , the density of aluminum nitride is 3.26 g / cm ³ , and the density of the mixture of Resin A and CRN is 1.20 g / cm ³ . It was 0.37 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening | curing agent was computed. Moreover, it was 64 volume% when the ratio of the 2nd filler with respect to the said total volume was computed. In addition, the ratio of the total volume of the 2nd filler and the 3rd filler with respect to the said total volume was 74 volume%.
Moreover, the average particle diameter (D50) of the 2nd filler was 24 micrometers.

Using the epoxy resin varnish obtained above, the hot press conditions by vacuum press were changed to press temperature: 150 ° C., vacuum degree: 1 kPa, press pressure: 1 MPa, treatment time: 60 seconds, and by vacuum press. The B-stage sheet and the resin with copper foil were the same as in Example 1 except that the vacuum pressure bonding conditions were changed to press temperature: 150 ° C., vacuum degree: 1 kPa, press pressure: 4 MPa, treatment time: 5 minutes. A cured product was prepared and evaluated in the same manner as described above.
The results are shown in Table 1.

(Example 4)
First filler (α-alumina, HIT-70) 0.45 mass%, second filler (boron nitride, HP-40) 70.29 mass%, thermosetting resin (resin B) 10.22 mass% Curing agent (CRN) 6.30% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 12.56% by mass. An epoxy resin varnish was obtained as a resin composition containing a solvent.

(Example 5)
First filler (α-alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 70.29% by mass, thermosetting resin (resin C) 10.34% by mass , Curing agent (CRN) 6.05% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 12.69% by mass. An epoxy resin varnish was obtained as a resin composition containing a solvent.

(Example 6)
First filler (α-alumina, HIT-70) 0.45 mass%, second filler (boron nitride, HP-40) 70.29 mass%, thermosetting resin (resin D) 10.42 mass% A curing agent (CRN) of 5.90% by mass, a curing accelerator (TPP) of 0.11% by mass, a silane coupling agent (KBM-573) of 0.07% by mass, and a solvent (CHN) of 12.76% by mass. An epoxy resin varnish was obtained as a resin composition containing a solvent.

(Example 6)
First filler (α-alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 74.23% by mass, thermosetting resin (resin A) 7.23% by mass Curing agent (CRN) 4.46% by mass, curing accelerator (TPP) 0.08% by mass, silane coupling agent (KBM-573) 0.07% by mass, and solvent (CHN) 13.48% by mass. An epoxy resin varnish was obtained as a resin composition containing a solvent.

The density of the alumina is 3.97 g / cm ³ , the density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of Resin A and CRN is 1.20 g / cm ³ . It was 0.27 volume% when the ratio of the 1st filler with respect to the total volume of a filler, a thermosetting resin, and a hardening | curing agent was computed. Moreover, it was 81 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

(Comparative Example 1)
Second filler (boron nitride, HP-40) 70.61% by mass, thermosetting resin (resin A) 10.26% by mass, curing agent (CRN) 6.34% by mass, curing accelerator (TPP) 0 .11 mass%, silane coupling agent (KBM-573) 0.07 mass%, and solvent (CHN) 12.61 mass% were mixed to obtain an epoxy resin varnish as a resin composition containing a solvent.

The density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of resin A and CRN is 1.20 g / cm ³ . The proportion of the filler was calculated to be 74% by volume.

A B stage sheet and a cured resin product with a copper foil were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above.
The results are shown in Table 2.

(Comparative Example 2)
Silica nanofiller (manufactured by Admatechs Co., Ltd., trade name: Admanano, average particle size: 15 nm) 0.25% by mass as the first filler, 70.49% by mass of the second filler (boron nitride, HP-40), Thermosetting resin (resin A) 10.22% by mass, curing agent (CRN) 6.30% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass % And 12.56 mass% of solvent (CHN) were mixed to obtain an epoxy resin varnish as a resin composition containing a solvent.

Density 2.20 g / cm ³ of silica, the density of boron nitride 2.18 g / cm ^3, and the density of the mixture of the resin A and the CRN as 1.20 g / cm ^3, a silica nanofiller and a second filler It was 0.26 volume% when the ratio of the silica nanofiller with respect to the total volume of a thermosetting resin and a hardening | curing agent was computed. Moreover, it was 74 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

(Comparative Example 3)
α-alumina filler (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-07, average particle size: 700 nm) 0.72% by mass, second filler (boron nitride, HP-40) 66.82% by mass, heat Curable resin (resin A) 12.65% by mass, curing agent (CRN) 3.90% by mass, curing accelerator (TPP) 0.13% by mass, silane coupling agent (KBM-573) 0.07% by mass And 11.81% by mass of a solvent (CHN) were mixed to obtain an epoxy resin varnish as a resin composition containing a solvent.

The density of the alumina is 3.97 g / cm ³ , the density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of Resin A and CRN is 1.20 g / cm ³ . The ratio of the α-alumina filler to the total volume of the filler, thermosetting resin and curing agent was calculated to be 0.40% by volume. Moreover, it was 69 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

(Comparative Example 4)
γ-alumina nanofiller (manufactured by Daimei Chemical Co., Ltd., trade name: TM-300D, average particle size: 10 nm) 0.45% by mass, second filler (boron nitride, HP-40) 70.29% by mass, Thermosetting resin (resin A) 10.22% by mass, curing agent (CRN) 6.30% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) 0.07% by mass % And 12.56 mass% of solvent (CHN) were mixed to obtain an epoxy resin varnish as a resin composition containing a solvent.

When the density of alumina is 3.97 g / cm ³ , the density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of resin A and CRN is 1.20 g / cm ³ , the γ-alumina nanofiller and the second The ratio of γ-alumina nanofiller to the total volume of the filler, thermosetting resin and curing agent was calculated to be 0.26% by volume. Moreover, it was 74 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

(Comparative Example 5)
First filler (α-alumina, HIT-70) 0.45% by mass, second filler (boron nitride, HP-40) 70.29% by mass, bisphenol A type epoxy resin (DIC ( Co., Ltd., trade name: EPICLON 850, no mesogenic group) 10.08% by mass, curing agent (CRN) 6.58% by mass, curing accelerator (TPP) 0.11% by mass, silane coupling agent (KBM-573) ) 0.07% by mass and 12.42% by mass of solvent (CHN) were mixed to obtain an epoxy resin varnish as a resin composition containing the solvent.

The density of alumina is 3.97 g / cm ³ , the density of boron nitride is 2.18 g / cm ³ , and the density of the mixture of bisphenol A type epoxy resin and CRN is 1.20 g / cm ³ , It was 0.26 volume% when the ratio of the 1st filler with respect to the total volume of a 2nd filler, a thermosetting resin, and a hardening | curing agent was computed. Moreover, it was 74 volume% when the ratio of the 2nd filler with respect to the said total volume was computed.

A B stage sheet and a cured resin product with a copper foil were prepared in the same manner as in Example 1 except that the epoxy resin varnish obtained above was used, and evaluated in the same manner as described above.
The results are shown in Table 2.
In Tables 1 and 2, “-” indicates no addition.

By combining a nanoparticle size alumina filler and a thermosetting resin having a mesogenic group in the molecule, the cured resin sheets of Examples 1 to 7 all showed high thermal conductivity. Further, in any of Examples 1 to 7, the thermal conductivity of the cured resin converted from the cured resin sheet is higher than the thermal conductivity of the cured resin obtained from the cured resin without filler. Indicated. From this, it was proved that the thermosetting resin having a mesogenic group exhibits higher order with the alumina filler as a nucleus, and the thermal conductivity of the cured resin itself is improved. In each of Examples 1 to 7, both the flow amount and the dielectric breakdown voltage were good.

In Comparative Examples 1, 2, and 4 in which the nano-sized alumina filler was not added, the thermal conductivity of the cured resin sheet was lower than that in Example 1, and the conversion from the cured resin sheet was also performed. The value of the thermal conductivity of the cured resin was lower than the thermal conductivity of the cured resin obtained from the resin cured product without filler. Moreover, also in the comparative example 5 using the general purpose epoxy resin which does not have a mesogenic group, compared with Example 1, the heat conductivity of the resin sheet cured | curing material was low. Further, in Comparative Example 3 in which the particle size of the alumina filler as the first filler was outside the range of 1 nm to 500 nm, the flow amount was remarkably reduced.

10 Second filler 20 First filler 30 Cured product made of thermosetting resin having mesogenic group 40 Filler other than α-alumina 50 Cured product made of thermosetting resin having no mesogenic group

Claims

The average particle size (D50) corresponding to 50% cumulative from the small particle size side of the weight cumulative particle size distribution is 1 nm to 500 nm, the first filler containing α-alumina, and the small particle size side of the weight cumulative particle size distribution A resin composition comprising a second filler having an average particle diameter (D50) corresponding to 50% cumulative from 1 μm to 100 μm, and a thermosetting resin having a mesogenic group in the molecule.
The resin composition according to claim 1, wherein the content of the first filler is 0.1% by volume to 10% by volume in the entire volume.
The resin composition according to claim 1 or 2, wherein the second filler includes a nitride filler.
The resin composition according to claim 3, wherein the nitride filler includes at least one selected from the group consisting of boron nitride and aluminum nitride.
The resin composition according to any one of claims 1 to 4, wherein the content of the second filler is 55% by volume to 85% by volume in the entire volume.
The resin composition according to any one of claims 1 to 5, wherein the thermosetting resin is an epoxy resin.
The resin composition according to any one of claims 1 to 6, wherein the mesogenic group has a structure in which three or more six-membered cyclic groups are connected in a straight chain.
The resin composition according to any one of claims 1 to 7, further comprising a phenol novolac resin.
9. The novolac resin according to claim 8, wherein the phenol novolac resin is a novolac resin containing a compound having a structural unit represented by at least one selected from the group consisting of the following general formulas (I-1) and (I-2). Resin composition.

[In General Formulas (I-1) and (I-2), R 1 independently represents an alkyl group, an aryl group, or an aralkyl group, and R 2 and R 3 each independently represent a hydrogen atom or an alkyl group. Represents an aryl group or an aralkyl group. Each m independently represents an integer of 0 to 2, and each n independently represents an integer of 1 to 7. ]
10. The resin composition according to claim 8, wherein the phenol novolac resin has a content ratio of a monomer composed of a phenol compound constituting the phenol novolak resin of 5% by mass to 80% by mass.
A semi-cured resin composition which is a semi-cured body of the resin composition according to any one of claims 1 to 10.
A cured resin composition which is a cured product of the resin composition according to any one of claims 1 to 10.
A resin sheet, which is a sheet-like molded body of the resin composition according to any one of claims 1 to 10.
The resin sheet according to claim 13, wherein the flow amount in a semi-cured state is 130% to 210%.
A prepreg having a fiber base material and the resin composition according to any one of claims 1 to 10 impregnated in the fiber base material.
An adherend, and the resin composition according to any one of claims 1 to 10, disposed on the adherend, the resin sheet according to claim 13 and claim 14, and claim 15. A laminate having a semi-cured resin composition layer that is at least one semi-cured material selected from the group consisting of the prepregs described in 1. or a cured resin composition layer that is a cured material.
At least one selected from metal foil, the resin composition according to any one of claims 1 to 10, the resin sheet according to claims 13 and 14, and the prepreg according to claim 15. A metal substrate in which a cured resin composition layer, which is one cured body, and a metal plate are laminated in this order.
At least one selected from a metal plate, the resin composition according to any one of claims 1 to 10, the resin sheet according to claims 13 and 14, and the prepreg according to claim 15. A printed wiring board in which a cured resin composition layer, which is one cured body, and a wiring layer are laminated in this order.